201245120 六、發明說明： 優先權主張 rnm 13/094,657 ^ 【發明所屬之技術領域】 >本發明廣泛地涉及將生產_的製程以及，特別是由 醇、水和醋酸乙酯之醇類混合物移除水之製轾。 3 【先前技術】 工業上使用的乙醇係以傳統方式由石化原料，如石油、天然氣 煤炭，由進料中間體，如合成氣，或由麟質原料材料或纖^原^ 材料’如玉米或甘薦，生產之。來自石油化工原料以及來自纖維素原 料的乙醇傳統生產方法，包括乙烯之酸催化水合、甲醇同系化、直接 醇合成和”費托合成”（Fischer-Tropschsynthesis)。不穩定性石化原料材 料價格會引起傳統方式生產乙醇的成本波動，#原料材料價格^上張 時’使得需要替代來源的乙醇生產更有所需求^澱粉原料以及纖維素 原料’可_發_化成為乙醇。但是’通f發酵是驗難性乙醇 生產，其係適合用於供作燃料或人類消費之用。此外，澱粉或纖維素 原料的發酵會和作為食物來源競爭’而限制乙醇可用於工業生產的量^ 經由烧酸類和/或其他羰基的化合物之還原來生產乙醇已被廣$泛 研究，以及觸媒，支撐體(supports)和操作條件之各種組合已在文獻中 被提及。於還原烷酸，如還原醋酸期間，其他化合物會與乙醇一起形 成或在副反應中形成。此等雜質限制了乙醇從此反應混合物之生產與 回收。例如’在氫化反應中’酯類會連同乙醇和/或水一起產出，而形 成為共沸物(azeotrope) ’其將是很難分離的。此外，當轉化不完全時， 未反應的醋酸會殘留在乙醇粗製品中’其必須移除以回收乙醇。 EP02060553說明一種轉化烴類化合物成乙醇的製程，其涉及轉化 201245120 k類化合物成乙酸以及氫化乙酸成乙醇。來自氫化反應器的物流係分 離以獲得乙醇流以及醋酸和醋酸乙醋之流，其係循環至氫化反應器。 自藉由還原舰如乙酸’及/或其他含縣化合物所得之粗產物以 回收乙醇之改良製程仍有需要。 【發明内容】 在第一實施方式中，本發明是針對一種生產乙醇的製程，其包括 於觸媒存在下在-反應器内氫化騎以形成乙醇粗製品；使一部份的 該乙醇粗製品在第-顏塔内分離以產出含醋_第—殘㈣及含乙 醇醋酸乙醋及水的第一顧出物；由一部份的該第一館出物移除水以 產出含有低於ίο重量％的水之乙醇混合物流；以及由該乙醇混合物流 回收乙醇。 在第二實施方式中，本發明是針對一種生產乙醇的製程，其包括 於觸媒存在下在-反應器内氫化⑽以形成乙醇粗製品；使一部份的 該乙醇粗製^在第-細勒分触產出含醋酸的第—雜物及含乙 醇、醋酸乙醋及水的第-餾出物；由該第一鶴出物移除水以產出乙醇 混合物流；以及使-雜的該乙醇混合驗在第二反應如分離以產 出含乙醇的第二殘留物及含醋酸乙酯的第二餾出物。 在第二實施方式中，本發明是針對一種回收乙醇的方法，其包括 提供含乙醇、醋酸、醋酸乙自旨，及水之乙醇粗製品；使—部份的該乙 醇粗製品在第_細_分離以產出含大部份錯酸的第—_物及含 各大部份的⑽和St酸乙S旨的第-軸物；由該第—軸物移除水以 產出含有低於10 «%的水之乙醇混合物流；以及由該乙醇混合物流 回收乙醇。 【發明說明】 本發明涉及在觸媒存在下經由氫化醋酸所產生的乙醇之回收製 程。氫化反應產生乙醇粗製品’該乙醇粗製品含有乙醇、水、錯酸乙 酯、未反應的醋酸，以及其他雜質。此等在反應混合物中化合物的濃 201245120 度係觸媒域及製雜件主钱时。然而，反應混合射水的濃度 並非由此等因素所支配，因為水係以大約1:1莫耳比共同生產於氫化 反應内。因而，生產額外的乙醇亦導致生產額外的水。 一在本發明的一實施方式中，該製程涉及將乙醇粗製品引進起始分 2洛館塔(第-蒸館塔)内，該起始分離蒸娜將該乙醇粗製品分離成 s乙醇、醋酸乙酯及水的第一餾出物，以及含水和未反應的醋酸的第 -殘留物。接而由該第—館出物移除水以形成乙醇混合物流，該乙醇 混2流較佳為含有低於1G重務的水，低於6重量％的水或低於4 重里％的水。就範圍而言，該乙醇混合物流含有從0.001至10重量％ 的^，例如：從0.01至6重量％的水或從01至4重量％的水。產物 乙醇接而_乙醇混合物流來回收。現在6經發現移除該起始蒸鱗 的餾出物内的水可以改善回收乙醇之整體分離效率。 水和乙醇於蒸館塔内形成不易分離的共滞物(azeotlOpe)。乙醇水 共彿物會因此使得蒸娜内可回收的乙醇受限制而成為含92_9 醇產物。不論其他化合物存在與否，要來處理蒸鶴塔内 column的制比處理共彿物會f要的能量更少的能量，導致水j 物内。接而使用水分離器而由财物移除水，此有利地需 ，比處理_塔内水/乙醇絲物更少的能量。因而，本發 氫化乙醇粗製品之低能量的方法且從而移除與乙醇共同生產財。； =出物内水的濃度取決於醋酸轉化率可能會有所不同 方式中，娜物包含的水4大於桃醇_物 Π = 4重量％，大於5重量％，或大於7重量％ 例如.大於 意地包含從4 4量％至38 4量％的水，例如：從=館出物隨 %的水，或從7重量％至25重量％的水。 里〇至32重量 因為館出物内水的濃度通常會大於工業或燃料級 接受的量’所以在本發明·财式巾，該製程奴=2可 大部份的切生產乙醇混合物。較佳者為 丨物移除很 量之有機物、醋酸乙酯或乙醛之前先移除水。 何可以察覺到的 也—實施方式中，水係 201245120 = 單舉例:言，蒸氣相(一。hase)議可引至 4皁708在一些實施方式中，餾出物可冷凝成液 眚^水的蒸發熱提供給餾出物以允許水滲透通過膜。在較佳 ’移除顧出物内至少·的水，例如：至少齡成水或至 ’該百分率係對館出物内的水總量而言。在更多的較佳實 Mvl以由，物移除9〇至"％的水。因而，所生成的乙醇混 :/舌旦3有較少量的水’從〇·01至10重量％的水，例如：從0.5 醇混從〇.5至4重量%的水。在某-實施方式中，乙 乙醇/ 縣軸的水量更少的水濃度。為了達成低於 明水量更之水濃度’财要大量·量。因而，本發 旦有利地由第—㈣物移除水以產出乙醇混合物而不需大量的能 ί期=移合物含較少的水’所以也減少在產物分離的後 實施方式中’在本製程之最初蒸德塔之能量需求可以低 #央制熱置單位每嘲精製的乙醇，例如：低於4·5百萬英制熱 精製的乙戟低於Μ百萬英職量單位每彌製的乙 ㈣旦财式巾，該製程可㈣更高·量需絲運作，設若 =里吊求係低於從觸出物之乙醇粗製品移除大部份的水，例 除該乙醇粗製品内之多於65%的水，所需的能量。 物移除的柯啊回至起始驗塔且最雜由殘留物而由 齡移除。在—實施方式巾’―部份移除的水可以冷凝且於乙 醇粗製品的進料處下方，例如接近起始難塔的底部，返回至起始基 娜。取決於水移除的技術，移除的水内可有-些乙醇和醋酸乙醋r 且因此可能希由錢少—部份移除的水返回至起始諸塔來回收 此等化η物。使移除的水細至触細塔可以增加域留物而被抽 回的水量。在其他實施方式中，—部份移除的水可以饋至用來由乙醇 物回收乙醇越之分離蒸瓣，例如輕齡蒸娜。麵份蒸館 塔内存在}里的水’例如低於1Q%的水，該百分率雜總進料而言， 其會在促進猶乙齡乙_分離上是有伽。該一雜需要被移除 201245120 的水可以經由系統而排除之。 乙醇混合物可以於輕餾份蒸餾塔内進一步加工來回收乙一 ，實施方式中，可能會輕料輕输細塔内相濃心 ： 分，器的類型，乙醇混合物可含有低於〇5重量％的水。為了控^ 的濃度’可以使用旁通管(by-passline)來分流顧出物。分流比可 所不同來控継_份_塔之進料_水量 ^ 流比可以在由HH至⑽的範圍，例如由5:1至1:5或^中^ 制水濃度時可以使用其他的分流比。騎騎_働物未予以= 移除水且可以組合以乙醇混合物或與乙醇混合物翻饋人至輕館份菜 顧塔。組合_出物與乙醇混合物具有_水濃度大於Μ重量％、，、、 例如，大於2重務或大於5重魏。就細而言，組合_出物盘 乙酵混合物之總水濃度可以為由〇.5至15重量％，例如由2至12重 量％ ’或由5 S 1G重魏。輕齡細塔之額外的水通常會盘乙醇一 起回收以及依希望來分離以提供乙醇產物。 本發明的製程可以使用適合的技術從細物移除水。舉例而言， =可以在冷凝前以氣相移出，歧以液相移^例如，可以使用二附 單元膜、力子篩、萃取蒸顧塔，或其等之組合來移除水。適合的吸 附單元包^壓變吸附(PSA)#元與熱變吸附(TSA)單元。吸附單元可以 包括分子筛，例如鋁矽酸鹽化合物。 也可使用膜或_敵來從館出物分離水。膜鱗舰組可以選 自於任何ι|合的膜’其雜夠自也含有乙醇無酸乙自旨之物流來移除 滲透水流之臈。 醋酸之氫化 口本發明的製程可以與用於生產乙醇之任何氫化的製程一起使用。 酸之機、麟、反絲料及分離製程係如以下 進一步說明的。 用於本發明製程的原料，醋酸和氫氣，可能來自任何合適的來源， 包括天然氣、石油、煤炭、生物料等。擧例而言，通過甲醇羰基化、 201245120 乙磐氧化、乙職化、氧化發酵、及厭紐料，可生產醋酸。合適 用於生產醋酸之甲醇载基化製程為美國專利第7,2〇8,624號；第 入115’772 號；第 7’005,541 號；第 6,657,078 號；第 6,627,77〇 號；第 6，143’930 號；第 5,599,976 號，·第 5，144,068 號；第 5,〇26 9〇8 號；第 5,001，259號；以及第4,994，_號中所描述 納入作為參考。視情況，乙醇之生產可以與此甲醇羰基化製程整合。 由於石油和天然氣變得波動，價格會忽起忽落，用於從備用碳源 來生產醋酸和巾間體如f醇和—氧化翻方法，已引起絲越大的興 趣。特別是當；5油價難對較高時，由更何得利關碳源所衍生的 合成氣("syngas")六生產醋酸可能會成為有利的。美國專利第6,232,352 號揭露改裝曱醇廠以生產醋酸的方法，其全文在此併入本文做為參 考。藉由改裝曱醇工廒，對於新建乙酸工廠所產生相關之較大成本， 以及伴隨而來的一氧化碳產生的問題，均可顯著地降低或大幅省去。 所有或部分合成氣係衍生自甲醇合成路徑，並將其供應至分離器單元 以回收一氧化碳，其接著被用以生產醋酸。以類似的方式，用於氫化 步驟之氫氣可以由合成氣來提供。 在一些實施方式中，以上所說明的醋酸氫化製程之一些或全部的 原料可以部份或全部地從合成氣所衍生。舉例而言，醋酸可以從曱醇 和一氧化碳所形成’二者均可從合成氣所衍生。合成氣可以藉由部份 氧化重組(oxidation reforming)或蒸氣重組(steam reforming)而形成，且 一氧化複可以從合成氣分離。類似地，用於氫化醋酸來形成乙醇粗製 品之步驟的氫氣可以由合成氣分離。合成氣又可以從多種碳源衍生。 碳源，舉例而言’可以選自於由天然氣、油 '石油、煤炭、生物料及 其等之組合所組成之群組。合成氣或氫氣也可以從生物衍生的甲烧氣 所獲得，如經由廢棄物掩埋場或農業廢棄物所產生的生物衍生的曱烷 氣。 在另一實施方式中’使用於氫化步驟中的醋酸可以從生物料的發 酵形成。發酵製程較佳者為利用產乙酸(acetogenic)製程或同型產乙酸 (homoacetogenic)微生物以發酵糖成為醋酸，而其會生產很少的，如果 201245120 有的話’二氧化碳為副產品。與傳統的酵母加工比較，其典型具有約 67°/〇的碳效率，發酵製程的碳效率其較佳者為大於7〇%、大於80%或 大於90%。可視情況而任擇地，使用於發酵製程中的微生物為一菌屬 (genus)，其係選自由梭菌屬(Clostridium)，乳酸桿菌屬，穆爾氏菌屬 (Moorella) ’熱厭氧桿菌屬（Thermoanaerobacter)，丙_酸桿菌屬 (Propionibacterium) ’ Propionispera，厭氧螺菌(Anaerobiospirillum)，及 擬桿菌屬(Bacteriodes)所組成之群組；以及特別是菌種(species)，其係 選自.由曱酿乙酸梭菌（Clostridium formicoaceticum)，路酸梭菌 (Clostridium butyricum) ’ 熱醋穆爾氏菌(Moorella thermoacetica)，飢伍 熱厭氧桿菌(Thermoanaerobacter kivui)，戴白氏乳酸桿菌(Lactobacillus delbrukii),產丙酸丙酸桿菌（pr〇pi〇nibacterium acidipr〇pi〇nici)， (Propionispera arboris)，產琥拍酸厭氧螺菌（Anaerobi〇spirUlum succinicproducens)，嗜殿粉擬桿菌(Bacteriodes amylophilus)及栖瘤胃擬 桿菌(Bacteriodes ruminicola)所組成之群組。可視情況地，於本製程中， 全部或部分之從生物料，例如木盼素(lignans)，而來的未發酵殘留物， 其可以被氣化以形成可用於本發明的氫化步驟中之氫氣。用於形成醋 酸之典型發酵製程揭示於美國專利第6,509，180號；第6,927,〇48號； 第 7,〇74,6〇3 號；第 7,5〇7,562 號；第 7,351，559 號；第 7,601，865 號； 第7,682,812號；及第7,888,082號之中，其全文在此納入作為參考。 亦參見美國專利申請公開案號2008/0193989與2009/0281354，其全文 在此納入作為參考。 生物料之實例包括但不限於，農業廢棄物，林產品、草、和其他 的織維素材料、伐木殘留物、軟木材碎片、硬木碎片、樹分枝、樹殘 幹、葉子、樹皮、鋸木屑、不合規格紙漿、玉米 '玉米蒿桿、小麥桿、 稻稈、甘蔗渣、柳枝稷、芒、動物廄肥、城市垃圾、城市污水、商業 廢棄物、葡萄渣(grape pumice)、杏仁殼、胡桃殼' 椰子殼、咖啡涪、 草粒、乾草粒、木頭粒、纸板、紙、塑膠以及布。參見，例如：美國 專利第7,884,253號，其全文在此納入作為參考。另一種生物料來源為 黑液，一種濃稠深色的液體，其為用於使木頭轉換成紙漿之^ 201245120 ϊϊϋί品，魏漿接而絲來製n黑液為木質素殘餘物、半纖 維素和無機化學品的水溶液。 牛纖 由户ί=發Γ專利細35,377，也納入在此做為參考，係提供一種 素物枓，如石油、煤炭、天然氣和生物料轉化成甲醇之生產方法。 將隨和/綠财素物料加讀化氣化) 氣體的方法，將該製減體進—步另加人天錢，進行蒸 二二以喊合絲^該合成氣轉化為甲醇’該甲醇可航而得醋酸:、 =至也可同樣地來產生氫氣’而氫氣則可如上所述使用於本發明 Ι=ϋη821，ιη號’其中揭示—種藉由氣化形成合成氣以轉 Γΐίί 製程，以及顏專 6,685,754號，其中揭示-種 生產3虱乳體組成物之製程，含氫氣體組成物係例如含氫氣與 碳之合成氣，以上其等之整體所示内容在此納人均做為參考。 輸送到氫化反應之醑酸也可包括其他羰酸類和酸肝類，以及乙搭 和_。較佳者為，合適的醋酸進料流包括一種或多 醋酸、醋酸酐、㈣、醋編旨，及其混合物所組成之群組。m ，的化合物也可在本發㈣程中被氫化。在—些實施方式中，紐的 存在’如丙酸或其酸軒的存在，也許會有利於丙醇之生產。水亦可以 存在於醋酸進料内。 另外，蒸氣形式的醋酸可從甲醇羰化單元之閃蒸塔取出，直接採 用為粗製品，此可參閱美國專利第6,657,078號中所描述的内容，其全 ，在此納入作為參考。舉例而言，蒸氣粗製品可直接饋入本發明之乙 醇合成反應區’而不需要冷凝醋酸和輕腑，或是移除水，而此可節 約整體的製程成本。 醋酸可在反應溫度蒸發(vap〇rized)，然後蒸發之醋酸可以隨著未 稀釋之，氣’或以相對惰性載氣，如氮、氬氣、氦氣、二氧化碳等稀 釋之氫讀人。為使絲在氣相巾進行，應控⑽、統㈣溫度不低於 醋酸的露點(dew point)。在-實施村巾，㈣可钱化反應器操作 壓力下於醋㈣點蒸發，然後蒸發之醋酸可進—步加熱到反應器入口 溫度。在實施方式巾’醋酸在絲前與其他氣體混合，其次加熱 201245120 混，条氣巧反應n人口溫度。其較佳者為，在溫度等於或低於 125 C，使氫氣和/或循環氣通過醋酸，其可使醋酸轉移成蒸氣態，隨 後再加熱合併後瘵氣流至反應器入口溫度。 醋酸氫化成乙醇製程的一些實施方式，可包括使用固定床反應器 或流化床反絲之多觀置。在本發明許多的實施方式巾，可以使用" 絕熱"反應#’也就是說，很少有或根本沒有必要在反舰通入内部管 道加熱或除^。在其它實施方式+，徑向流統應减反應器組可以 使用，或一系列的反應器可以使用，無論其具有或不具有熱交換，淬 ^，或引進更多的進料。另外，可以使用具有傳齡f之管殼式反應 器。在許多情況’反應區可安置在單―容器或熱找器介人其中系列 的容器組之内。 、在優選的實施方式巾，觸媒會被用於固定床反應器巾，例如呈管 道或管形狀之反應器，其巾反麟財喊氣的形絲傳遞或通過觸 媒。可以採用其他反應器’如流化或奔放床反應器。在某些情況下， 氫化觸媒可同時配闕性物料，以調節反應物流通過觸媒床之壓降和 反應物與觸媒顆粒的接觸時間》 氫化反應可以在液相或氣相進行。較佳為在下列情況下進行氣相 反應。反應溫度可介於125°C至350°C，例如：從2〇〇°C至325°C，從 225C至300C左右’或從25(TC至300°C。氫化反應器的操作溫度通 常比酯化反應器為尚。壓力範圍從1〇千帕(砂幻至3,〇〇〇千帕，例如： 從50千帕至2,300千帕，或從1〇〇千帕至1500千帕。反應物饋入反 應器的蒸氣每小時空間速度（GHSV)可為大於500/小時，例如：大 於1000/小時’大於2500/小時，甚至大於5000/小時。就範圍而言， GHSV可以從50/小時至50,000/小時，例如：從5〇〇/小時至3〇,〇〇〇/小 時’從1000/小時至1〇,〇〇〇/小時’或從1〇〇〇/小時至65〇〇/小時。201245120 VI. Description of the invention: Priority claim rnm 13/094,657 ^ [Technical field of the invention] > The present invention broadly relates to the process of producing and, in particular, the alcohol mixture of alcohol, water and ethyl acetate In addition to the water system. 3 [Prior Art] The ethanol used in the industry is traditionally derived from petrochemical feedstocks such as petroleum and natural gas coal, from feed intermediates such as syngas, or from linden raw materials or fibers such as corn or Gan recommended, production. Conventional production processes for petrochemical feedstocks and ethanol from cellulosic feedstocks include ethylene acid catalyzed hydration, methanol homologation, direct alcohol synthesis and Fischer-Tropsch synthesis. The price of unstable petrochemical raw material materials will cause the cost fluctuation of the traditional way of producing ethanol. #原料材料的质量@上张时' makes the need for alternative sources of ethanol production more demanding ^starch raw materials and cellulose raw materials' can be _ _ Become ethanol. However, fermentation is a test for ethanol production, which is suitable for use as a fuel or for human consumption. In addition, the fermentation of starch or cellulose raw materials competes with food sources to limit the amount of ethanol that can be used in industrial production. The production of ethanol via the reduction of acid-burning and/or other carbonyl compounds has been widely studied and touched. Various combinations of media, supports and operating conditions have been mentioned in the literature. During the reduction of the alkanoic acid, such as the reduction of acetic acid, other compounds may be formed with or formed in the side reaction. These impurities limit the production and recovery of ethanol from this reaction mixture. For example, 'in a hydrogenation reaction' esters will be produced together with ethanol and/or water to form an azeotrope which will be difficult to separate. In addition, when the conversion is incomplete, unreacted acetic acid will remain in the crude ethanol product, which must be removed to recover the ethanol. EP 0 020 553 describes a process for converting a hydrocarbon compound to ethanol which involves converting a 201245120 k class of compound to acetic acid and hydrogenating acetic acid to ethanol. The stream from the hydrogenation reactor is separated to obtain an ethanol stream and a stream of acetic acid and ethyl acetate which is recycled to the hydrogenation reactor. There is still a need for an improved process for recovering ethanol by reducing the crude product obtained from a ship such as acetic acid' and/or other county-containing compounds. SUMMARY OF THE INVENTION In a first embodiment, the present invention is directed to a process for producing ethanol comprising hydrogenating in a reactor in the presence of a catalyst to form a crude ethanol product; and making a portion of the crude ethanol product Separating in the first-Yanta tower to produce the first take-up of vinegar------(four) and ethyl acetate-containing acetic acid and water; removing water from a part of the first museum to produce a stream of ethanol mixture of water below ίο % by weight; and recovering ethanol from the stream of ethanol mixture. In a second embodiment, the present invention is directed to a process for producing ethanol comprising hydrogenating (10) in a reactor in the presence of a catalyst to form a crude ethanol product; and making a portion of the ethanol crude in the first Distilling the first impurity containing acetic acid and the first distillate containing ethanol, ethyl acetate and water; removing water from the first crane to produce a mixture of ethanol; and The ethanol mixture is subjected to a second reaction such as separation to produce a second residue containing ethanol and a second distillate containing ethyl acetate. In a second embodiment, the present invention is directed to a method for recovering ethanol, which comprises providing a crude product containing ethanol, acetic acid, acetic acid, and water, and a crude portion of the ethanol in the first Separating to produce a first-axis containing a majority of the wrong acid and a major-axis containing a majority of (10) and St-acid S; removing water from the first-axis to produce a content below 10 «% of the ethanol mixture stream of water; and the ethanol stream is recovered from the ethanol mixture stream. SUMMARY OF THE INVENTION The present invention relates to a process for recovering ethanol produced by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction produces a crude ethanol product. The crude ethanol product contains ethanol, water, ethyl acid block, unreacted acetic acid, and other impurities. When the concentration of the compound in the reaction mixture is 201245120 degrees, the catalyst field and the miscellaneous pieces are the main money. However, the concentration of the reaction mixture jet is not governed by such factors as the water system is co-produced in the hydrogenation reaction at about 1:1 molar ratio. Thus, the production of additional ethanol also results in the production of additional water. In one embodiment of the present invention, the process involves introducing a crude ethanol product into a starting column (the first steaming tower), and the initial separation steaming separates the crude ethanol product into s ethanol. The first distillate of ethyl acetate and water, and the first residue of aqueous and unreacted acetic acid. The water is removed from the first library to form an ethanol mixture stream, preferably containing less than 1G of water, less than 6% by weight of water or less than 4% by weight of water. . In terms of ranges, the ethanol mixture stream contains from 0.001 to 10% by weight, for example from 0.01 to 6% by weight of water or from 01 to 4% by weight of water. The product is recovered by ethanol and _ ethanol mixture. It has now been found that removal of water from the distillate of the initial steaming scale improves the overall separation efficiency of the recovered ethanol. Water and ethanol form a non-separable co-stagnation (azeotlOpe) in the steaming tower. Ethanol water will therefore limit the amount of ethanol that can be recovered in the steam to the 92-9 alcohol product. Regardless of the presence or absence of other compounds, it is necessary to treat the column in the steaming tower to process less energy than the energy required to cause the water to be in the water. The water separator is then used to remove water from the property, which advantageously requires less energy than the water/ethanol filaments in the column. Thus, the low energy process of the crude hydrogenated ethanol product and thus the co-production of ethanol. ; = The concentration of water in the product depends on the acetic acid conversion rate may vary. The water contained in the Na is 4 is greater than the peach alcohol _ material Π = 4% by weight, greater than 5% by weight, or greater than 7% by weight. More than intentionally, water is contained in an amount of from 4 to 384% by volume, for example, from = water of the museum, or water of from 7 to 25% by weight. Lieutenant to 32 weights Because the concentration of water in the library is usually greater than the amount accepted by the industrial or fuel grades, in the invention, the processing slaves can be used to produce most of the ethanol mixture. Preferably, the water is removed prior to removal of substantial amounts of organics, ethyl acetate or acetaldehyde. What can be perceived - in the embodiment, the water system 201245120 = single example: say, the vapor phase (a.hase) can be led to 4 soap 708. In some embodiments, the distillate can be condensed into liquid 眚 water The heat of vaporization is supplied to the distillate to allow water to permeate through the membrane. Preferably, at least the water in the reject is removed, e.g., at least aged water or to the percentage is the total amount of water in the exhibit. In more good real Mvl, the object removes 9〇 to "% of water. Thus, the resulting ethanol is mixed: / tongue 3 has a smaller amount of water 'from 〇·01 to 10% by weight of water, for example, from 0.5 to 5% to 4% by weight of water. In a certain embodiment, the water concentration of the ethanol/county shaft is less. In order to achieve a water concentration lower than the amount of water, the amount of money is large. Thus, it is advantageous to remove water from the -(d) material to produce an ethanol mixture without requiring a large amount of energy = the transfer compound contains less water 'and therefore also reduce the post-product separation in the embodiment' At the beginning of the process, the energy demand of the steaming tower can be low. The central heating unit sets every sneaked ethanol. For example, less than 4.5 million British hot refined 戟 戟 is less than Μ million British metric units. Benefied B (four) Dan-style towel, the process can be (four) higher and the amount of wire required to operate, set if the rigging system is lower than the removal of most of the water from the ethanol extract of the extract, for example, the ethanol More than 65% of the water in the crude product, the energy required. The removed Ke returned to the original tower and was most often removed from the residue by age. The partially removed water can be condensed and returned below the feed of the crude ethanol product, for example near the bottom of the starting tower, back to the starting base. Depending on the technique of water removal, the removed water may have some ethanol and ethyl acetate r and therefore may be less expensive - some of the removed water is returned to the starting towers to recover the η . The amount of water that is removed by making the removed water fine to the pinch tower can increase the domain residue. In other embodiments, the partially removed water can be fed to the vaporized flap for recovery of the ethanol from the ethanol, such as a lighter steaming. The water in the steaming tower is, for example, less than 1Q% of water, which is a gamma in the promotion of the age. This miscellaneous need to be removed 201245120 water can be excluded through the system. The ethanol mixture can be further processed in the light fraction distillation column to recover the first phase. In the embodiment, the inner phase of the fine column may be lightly and lightly transferred: the type of the device, the ethanol mixture may contain less than 5% by weight. water. In order to control the concentration ', a bypass-by-passline can be used to divert the material. The split ratio can be different. _ _ _ tower feed _ water volume ^ flow ratio can be used in the range from HH to (10), for example, from 5:1 to 1:5 or ^ water concentration can be used Split ratio. Ride _ 働 未 予以 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The combination_exit and ethanol mixture has a water concentration greater than Μ% by weight,, for example, greater than 2 weights or greater than 5 weights. In summary, the total water concentration of the combined-exit tray fermentation mixture may range from 〇5 to 15% by weight, for example from 2 to 12% by weight or from 5 S 1G. The additional water from the lighter column is typically recovered from the ethanol and separated as desired to provide the ethanol product. The process of the present invention can remove water from the fines using suitable techniques. For example, = can be removed in the gas phase prior to condensation, and the liquid phase can be shifted. For example, water can be removed using a combination of a unit membrane, a force sieve, an extraction steam column, or the like. Suitable adsorption units include pressure swing adsorption (PSA) #元 and thermal sorption adsorption (TSA) units. The adsorption unit may comprise a molecular sieve such as an aluminosilicate compound. It is also possible to use a membrane or an enemy to separate water from the museum. Membrane scales can be selected from any membranes that contain a stream of ethanol-free acid to remove the permeate stream. Hydrogenation of Acetic Acid The process of the present invention can be used with any hydrogenation process for the production of ethanol. The acid machine, the lining, the reverse yarn and the separation process are further described below. The feedstock used in the process of the present invention, acetic acid and hydrogen, may come from any suitable source, including natural gas, petroleum, coal, biomass, and the like. For example, acetic acid can be produced by methanol carbonylation, 201245120 acetamidine oxidation, ethylation, oxidative fermentation, and anaerobic materials. Methanol-based processes suitable for the production of acetic acid are disclosed in U.S. Patent No. 7,2,8,624; No. 115'772; No. 7'005,541; No. 6,657,078; No. 6,627,77; No. 6,143 '930, pp. 5, 599, 976, pp. 5, 144, 068; 5, 〇 26 9-8; 5, 001, 259; and 4,994, _ are incorporated by reference. Depending on the situation, ethanol production can be integrated with this methanol carbonylation process. As oil and natural gas fluctuate, prices fluctuate and fall, and the use of alternative carbon sources to produce acetic acid and towels, such as the f-alcohol and oxidizing methods, has caused greater interest in silk. Especially when the oil price is difficult to be higher, it may be advantageous to produce acetic acid ("syngas") from the carbon source derived from the carbon source. A method of converting a sterol plant to produce acetic acid is disclosed in U.S. Patent No. 6,232,352, the disclosure of which is incorporated herein by reference. By modifying the sterol process, the associated costs associated with new acetic acid plants, and the attendant carbon monoxide generation problems, can be significantly reduced or substantially eliminated. All or part of the syngas is derived from the methanol synthesis pathway and is supplied to a separator unit to recover carbon monoxide, which is then used to produce acetic acid. In a similar manner, the hydrogen used in the hydrogenation step can be provided by syngas. In some embodiments, some or all of the feedstock of the acetic acid hydrogenation process described above may be derived, in part or in whole, from syngas. For example, acetic acid can be formed from both sterol and carbon monoxide, both of which can be derived from syngas. The syngas can be formed by partial oxidation reforming or steam reforming, and the mono-oxidation can be separated from the syngas. Similarly, the hydrogen used to hydrogenate acetic acid to form a crude ethanol product can be separated from the syngas. Syngas can in turn be derived from a variety of carbon sources. The carbon source, for example, may be selected from the group consisting of natural gas, oil 'oil, coal, biomass, and the like. Syngas or hydrogen can also be obtained from biologically derived formazan gas, such as biologically derived decane gas produced through waste landfills or agricultural waste. In another embodiment, the acetic acid used in the hydrogenation step can be formed from the fermentation of the biomass. Preferably, the fermentation process utilizes an acetogenic process or homoacetogenic microorganisms to ferment sugar into acetic acid, which will produce very little, if 201245120, carbon dioxide is a by-product. Compared to conventional yeast processing, it typically has a carbon efficiency of about 67°/〇, and the carbon efficiency of the fermentation process is preferably greater than 7〇%, greater than 80%, or greater than 90%. Optionally, the microorganism used in the fermentation process is a genus, which is selected from the group consisting of Clostridium, Lactobacillus, Moorella, Thermoanaerobacter Genaerobacter, a group consisting of Propionispera, Anaerobiospirillum, and Bacteriodes; and especially species, selected from the group consisting of Clostridium formicoaceticum, Clostridium butyricum 'Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus Delbrukii), pr〇pi〇nibacterium acidipr〇pi〇nici, (Propionispera arboris), Anaerobi〇spirUlum succinicproducens, Bacteriodes amylophilus And a group consisting of Bacteriodes ruminicola. Optionally, in the present process, all or part of the unfermented residue from the biomass, such as lignans, can be gasified to form hydrogen which can be used in the hydrogenation step of the present invention. . A typical fermentation process for the formation of acetic acid is disclosed in U.S. Patent No. 6,509,180; No. 6,927, No. 4; No. 7, No. 74, No. 6, No. 7, 5, 7,562; No. 7,351,559; No. 7, 601, 865, No. 7, 682, 812, and No. 7, 888, 082, the entire disclosure of which is incorporated herein by reference. See also U.S. Patent Application Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are hereby incorporated by reference. Examples of biological materials include, but are not limited to, agricultural waste, forest products, grasses, and other weaver materials, harvested residues, softwood chips, hardwood chips, tree branches, tree residues, leaves, bark, saws Sawdust, substandard pulp, corn 'bean stalk, wheat stalk, rice stalk, bagasse, switchgrass, awn, animal manure, municipal waste, municipal sewage, commercial waste, grape pumice, almond shell, walnut Shell 'coconut shell, coffee pot, grass, hay, wood grain, cardboard, paper, plastic and cloth. See, for example, U.S. Patent No. 7,884,253, the disclosure of which is incorporated herein by reference. Another source of biological material is black liquor, a thick dark liquid, which is used to convert wood into pulp. 201245120 ϊϊϋ 品, Wei pulp is used to make n black liquor as lignin residue, semi-fiber An aqueous solution of a chemical and an inorganic chemical. Niu Fiu is a production method for the conversion of petroleum, coal, natural gas and biomass into methanol. The method of adding the gas to the accommodating/greening material to read the gasification, the method of reducing the body into the step of adding another person's money, steaming the second two to shout the wire ^ the synthesis gas is converted into methanol 'the methanol Acetate can be obtained by aerobics:, = can also produce hydrogen in the same way, and hydrogen can be used in the present invention as described above. Ι ϋ 821 821, ιη ', which discloses that the synthesis gas is formed by gasification to transfer ίί process And Yan, No. 6,685,754, which discloses a process for producing a 3-inch emulsion composition, such as a synthesis gas containing hydrogen and carbon, the contents of which are generally described herein as reference. The tannic acid delivered to the hydrogenation reaction may also include other carboxylic acids and acid livers, as well as yttrium and y. Preferably, a suitable acetic acid feed stream comprises one or more of acetic acid, acetic anhydride, (iv), vinegar, and mixtures thereof. The compound of m , can also be hydrogenated in the process of the present invention. In some embodiments, the presence of a neon such as propionic acid or its acid may be beneficial to the production of propanol. Water can also be present in the acetic acid feed. Alternatively, the acetic acid in vapor form can be removed from the flash column of the methanol carbonylation unit and used directly as a crude product, as described in U.S. Patent No. 6,657,078, the disclosure of which is incorporated herein by reference. For example, a crude vapor product can be fed directly into the ethanol synthesis reaction zone of the present invention without the need to condense acetic acid and flick, or remove water, which can reduce overall process cost. The acetic acid can be vap〇rized at the reaction temperature, and the evaporated acetic acid can be read with undiluted, gas or a relatively inert carrier gas such as nitrogen, argon, helium, carbon dioxide or the like. In order to make the silk in the gas phase towel, the temperature of the (10) and the system (4) should be controlled not lower than the dew point of the acetic acid. In the implementation of the village towel, (4) the reactor can be operated under pressure to evaporate at the vinegar (four) point, and then the evaporated acetic acid can be heated to the reactor inlet temperature. In the embodiment, the acetic acid was mixed with other gases before the wire, and then heated at 201245120, and the gas reacted n to the temperature of the population. Preferably, at a temperature equal to or lower than 125 C, hydrogen and/or recycle gas is passed through the acetic acid which converts the acetic acid to a vapor state, followed by heating and combining the helium gas stream to the reactor inlet temperature. Some embodiments of the hydrogenation of acetic acid to ethanol process may include the use of a fixed bed reactor or a fluidized bed. In many embodiments of the present invention, it is possible to use "insulation" reaction #', that is, there is little or no need to heat or remove the anti-ship into the internal pipe. In other embodiments +, the radial flow reduction reactor group can be used, or a series of reactors can be used, with or without heat exchange, quenching, or introducing more feed. Alternatively, a shell-and-tube reactor having an age of f can be used. In many cases, the reaction zone can be placed in a container group of a single container or a thermal seeker. In a preferred embodiment, the catalyst is used in fixed bed reactor wipes, such as reactors in the form of tubes or tubes, which are passed over or passed through a catalyst. Other reactors such as fluidized or bunk bed reactors can be employed. In some cases, the hydrogenation catalyst can be simultaneously formulated to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactants with the catalyst particles. The hydrogenation reaction can be carried out in the liquid phase or in the gas phase. It is preferred to carry out the gas phase reaction under the following conditions. The reaction temperature may range from 125 ° C to 350 ° C, for example: from 2 ° C to 325 ° C, from about 225 C to about 300 ° ' or from 25 (TC to 300 ° C. The operating temperature of the hydrogenation reactor is usually higher than The esterification reactor is still available. The pressure ranges from 1 〇 kPa (sand magic to 3, 〇〇〇 kPa, for example: from 50 kPa to 2,300 kPa, or from 1 kPa to 1500 kPa. The vapor hourly space velocity (GHSV) fed into the reactor may be greater than 500/hour, for example: greater than 1000/hour 'more than 2500/hour, or even greater than 5000/hour. In terms of range, GHSV may be from 50/hour. Up to 50,000 / hour, for example: from 5 〇〇 / hour to 3 〇, 〇〇〇 / hour 'from 1000 / hour to 1 〇, 〇〇〇 / hour ' or from 1 〇〇〇 / hour to 65 〇〇 / hour.
氫化係選擇性地在剛好足以克服在所選蒸氣每小時空間速度通過 催化床的壓降之壓力下進行’雖然沒有禁用較高的壓力，但不言而喻， 在高空間速度，例如：5000/小時，或6,500/小時通過反應器床可能會 遇到相當大的壓降。 S 11 201245120 雖然每莫秘酸聽雜^料歧，生產—莫耳的乙醇， 實際在進巾統觸酸之莫耳比可能會有料同：從約1〇〇:丄 至1 · 100 ’例如.從50 . 1至1 : 5〇，從2〇 : i至i : 2，或從12 : 1至1 :卜最佳為氫氣對醋酸之莫耳比大於2 :卜例如：大於 或大於8: 1。 time)也雜大的不同，此取決於酷 酸量’觸媒’反應H ’溫度和壓力等轉魏。典型的接觸時間範圍 從不到1秒’職则、時以上，若使職定床以外的觸媒系統，氣相 反應首選接觸時間至少為在從αι秒和刚秒之間，例如：從〇 3至 80秒或0,4至30秒。 #醋酸之氣化來形成乙醇較佳者為於氫化觸媒存在下實施。合適的 氫化觸媒包括-種_，其包含第―金屬和㈣的-種或更錄的第 -金屬，第三金屬紐條量的其他金屬，隨意承載於麟支撑體上。 第-金屬和隨意的第二金屬和第三金屬可以選自包含元素週期表取 =，IIIB，IVB，VB，VIB，卿，或篇族過渡金屬，鑭系金屬釣系金 屬之群組或選自元素週期表祖，IVA，VA，或VIA族之群組的任何金 屬。一些典型觸媒組成物中優選的金屬組合選自链/錫、翻/釕、链/鍊、 鈀/釕、鈀/銖、鈷/鈀、結/銘、钻/絡、麵/舒、始/錫、銀/把、銅/妃、銅 f、錄/把、金/把、釕/铼及釕/鐵。典型觸媒進一步記載於美國專利號 ^7’608,744號與美國專利申請公開案號2〇1〇/〇〇29995，其全部内容在 ^b、’内入作為參考。在另—實施方^巾’觸媒包括類型的觸媒 盲己載於美國專利中請公開案號厕/鳴獅，其全部内容在此納入作 為參考。 在-實施方式中，觸媒包括第一金屬，選自由銅、鐵、始、錄、 =錢、，”、紐 '鈦、鋅、鉻、銖、齡鎢所組成之群組。 =佳者為第-金屬選自由m錄和釕所組成之群組。更優選 為第-金屬選自麵^在本發明之實施方式中，當第—金屬係銘， 。二佳，為觸媒中齡量低於5重量％，如低於3重4%絲於i重量 〇，這是由於鉑的高度商業需求所致。 12 201245120 如上所述’在-些實施方式巾，該麟還包括第二金屬，立通常 會作為-種促進劑。如果存在的話，第二金屬較佳者為選自由銅、钥、 mmt'm猛、釕、鍊、金及鎮所 組成之群組。更佳者為，第二金屬選自由銅、錫、始 之群組。更佳者為，第二金屬選自踢及銶。 銲厅、成 在某些實施方式巾，當觀包括兩種或更多種的金屬，例如第一 金屬和第二金>1，職-金翻量可㈣丨重量％至lG重秋 從αι重量駐f重量％，或從〇·ι重频至3重量％。第二金屬較佳 的用量從Gj重量％至20重量％，例如從Q1重量％至1()重量％，或 者從0.1重里％至5重置％。對於含兩種或兩種以上金屬的觸媒而:， IS多種的金屬可以是互為合金，或是可包括非合金之金屬‘液 較佳的金屬比例可能略有不同，取決於使用在觸 類。在-些典型實施方式中，第一金屬對第二金屬的莫耳比== 10:1至Π，例如:從4:1至1:4,從2:1至1: 為1 至 1 : 1·5，或從 1.1 ·· 1 至丨：u。 1 ，媒亦可包括第工金屬’第三金屬可以選自上關出的任何第一 金屬或第二金屬’只要第三金屬不同於第—金屬和第二金屬二者 可。在較佳態樣中，第三金屬是選自由始、把、釘、銅、辞 ^鍊所組成之群組。尤麵第三金屬選㈣、缺訂。如果存在時 總重量較做0.05重量％至4重魏，例如：從= 至3重量％’級αι重量％至2重量. 董里/ =了-種或更多種的金屬外，在本發明之一些實施方式中， “立ν包括支撐體或改質支樓體。本文中所使用的術語“改質支^體 祕—切财仰域航賴，财_^支 支樓體或改f捕體⑽重量紐麵舰重量的7 =重秋，例如：從％重魏至97重量％，或從8〇重〇 重直I在使用改質姐體的首選實麵方式中，支撐體改性劑含9量5 201245120 為=媒總重量的（u重量％至5G重量％，例如：從Q 2重量％至25 重1/6由G.5重至15重量％，或從丨重量％至8重量％。觸媒 =金屬可分散在整個的支樓體，成層形成在整個的支撲體，包覆在支 撐體的外層（即’蛋殼狀外殼），或塗佈在支撐體的表面上。 對此領域之熟悉普通技藝者即知選擇支樓體材料，使得該觸媒體 系在用來形成乙醇的製程條件下具錢當活性，選擇性和穩定強勁性 (robust)。 適當的支推體材料可包括，例如：穩定的金屬氧化物為基礎的支 撑體或喊系支撑體。較佳的域體包括含教龍，如二氧化石夕、 yb石夕/氧化紹、ΠΑ族石夕酸鹽，如偏石夕酸約、熱解二氧化石夕、高純度 -氧切及其混合物。其他的讀體可包括，但秘錄化鐵、氧化 銘、二氧化鈦、氧化錯、氧化鎖、碳、石，墨、高表面積石墨化炭、活 性炭及其之混合物。 、如上所述，觸媒的支撐體可用支撐體改性劑改質。在一些實施方 式中，支撐體改性劑可以為酸性改性劑，其增加觸媒的酸性。合適的 酸性支撐體改性劑可以選自由週期表IVB族金屬氧化物，週期表^ 族金屬氧化物，週期表VIB族金屬氧化物，週期表VIIB族金屬氧化 物，週期表VIIIB族金屬氧化物，氧化銘，及其之混合物所組成之群 組。酸性支樓體改性劑包括選自由Ή〇2，Zr〇2，灿2〇5，Ta2〇5，Ai2〇3， B2〇3 ’ P2〇5，以及Sb2〇3所組成之群組。較佳的酸性支撐體改性劑包 括選自由Ti〇2 ’ Zr〇2 ’ Nb2〇5，恥〇5，以及Al2〇3所組成之群組。酸 性改性劑也可以包括 W〇3，Mo〇3，Fe2〇3，Cr2〇3，V2〇5，_&，Cu〇， C〇2〇3，以及Bi2〇3所組成之群組。 在另一實施方式中，支撐體改性劑可以為低揮發性或無揮發性的 鹼性改性劑。此種的鹼性改性劑，例如：可以選自由（i)鹼土氧化物， (11)驗金屬氧化物’（iii)鹼土金屬偏矽酸鹽《iv；)鹼金屬偏矽酸鹽， (v)週期表ΠΒ族金屬氧化物，（vi)週期表jjB族金屬偏矽酸鹽，（νΠ) 週期表ΙΠΒ族金屬氧化物，（viii)週期表IIIB族金屬偏矽酸鹽，及其 此合物所組成之群組。除氧化物和偏矽酸鹽外，亦可使用包括硝酸鹽、 14 201245120 亞墙酸鹽、猶鹽和乳酸鹽之其他麵的改_。切财性劑較佳 者為選自㈣、鉀、鎂、H綠鋅之任—者的氧化物和偏石夕酸 鹽’以及任何上述的混合物所組成之群組。更佳者為驗性支擇體改性 劑是石夕_ ’以及纟至更佳者為偏魏柳asiQ3)。如秘性支撑體 改性劑包括偏#赖，較佳者為至少部分的偏♦峡呈結晶的形式。 杈佳的二氧化矽支撐體材料是來自Saint-Gobain NorPro之 ss6ii38 高，面（hsa：> 的二氧化補媒載體。此 Saint_G〇bainN〇rPr〇 SS611；38二氧化魏現下列性質：包含約％ 的高表面積二氧化 夕’表面積、力250平方米/克，以汞式孔隙分析儀測定得中位孔徑約u 奈来，平均孔隙體積約L〇立方厘米/克；及堆積密度（paddngden卿） 約0.3S2公克/立方厘米（η碎/立方呎）。 _ ^較佳的氧化石夕/氧化鋁支撐體材料是來自Sud Chemie之Μ _⑽ 二氧化梦’具有標稱直㈣5絲，密度約G 562克/毫升，吸收度約 0.583^克水/克支樓體，表面積約16〇至175平方来/克，和孔隙體積約 0.68毫升/克。 .本發明觸媒組成物較佳者為將改質支樓體浸潰金屬（_ ㈣啊㈣而得，但其他製程，如化學氣相沉積v啊 dep_〇n)也可使用。這樣的浸潰技術描述在美國專利號入刪，⑽和 7,863,489以及美國專利申請公開案號2〇1_97485，盆全 納入作為參考。 '、 特別是’酷酸氫化可達到良好的醋酸轉化率和良好的乙醇選擇率 ΐί率1為本發明的目的，”轉化率”—詞是指在進料中醋酸轉化為 曰1以外制t合物之比率。轉化率細純料巾魏莫耳數之百分率 表不。轉化率可為至少剛’例如：至少有，至少有轉，至 ’至少有6G% ’至少有7()%或至少有戰。雖蘭媒具有 較冋的轉鱗是可取的，如至少有8G喊至少有9哪，但在一些實施 方式^转乙醇有高選神，職低的轉化率可以接受。在許多情 容易轉’通過適#_環流或使賴大的反應器即可補 乜轉化率，但彌補低選擇率則更難。 15 201245120 獅細轉化觸酸之料百分縣*。應該認朗每一種由 ~b合物具有社的選料，而獅率和齡率分別為獨立 的。舉例而言，如果轉化的醋酸之6G莫耳％轉化為乙醇 的選擇率為60%。較佳者為，链软門知乙醇 着^ 者為顧對乙氧基化合物之選擇率至少右 m至対職，或至対轉。本文帽制的術語 i擇具體指化合物乙醇’乙醛和醋酸乙醋。較佳者為乙醇的 ^擇率在8(U以上’例如：至少有85%或至少有88%。氫化製 ，如抵，⑽和二氧化碳有較 低之選擇率^些不被期待的產物的選擇率較 於1%。更佳者為檢測不到這些不被期待的產物 形成可此會疋低的’且理想上通過觸媒之低於2%，低於1%，或低於 0.5/的醋轉化為舰，而舰除了作為燃料外沒有多大價值。-、 ii中所使用的術語“產率，，是指氫化過程中每公斤觸媒每小時 所形成特疋的產物，如乙醇，的克數。產率每公斤觸縣小時產出至 >、有1〇〇克乙醇，例如··每公斤觸媒每小時至少有姻克乙醇，每公 斤，，每小時至少有_紅醇，佳的。以範_言，產率較佳 為是每公斤觸媒每小時產出100至3，_克的乙醇，例如：每公斤觸 媒每小時至2,则克的乙醇或是每公斤觸媒每小時6⑻至2_ 克的乙醇。 ’ 於本發明的條件下操作可導致以每小時至少〇1噸. 乙醇生產’例如：每小時至少i _乙醇，每小時至少5 ^的U的 或每小時至少10噸的乙醇生產。更大規模的乙醇工業生產，取決於規 模，一般應為每小時至少1嘲的乙醇，例如：每小時至少15領的乙醇 或每小時至少30噸的乙醇'就範圍而言，大規模的乙醇工業生產’本 發明的製程可以生產每小時從(U至160噸的乙醇，例如：每小時從 15至160噸的乙醇或每小時從3〇至8〇噸的乙醇。從發酵生產乙醇， 由於經濟上的規模，通常不允許以單一設施來生產乙醇，單一設施的 乙醇生產則可以藉由使用本發明的實施方式而達到。 在本發明不同的實施例方式中，由氫化製程所得的乙醇粗製品，The hydrogenation system is selectively carried out under pressure just enough to overcome the pressure drop across the catalytic bed at the selected vapor hourly space velocity 'although the higher pressure is not disabled, but it goes without saying that at high space velocities, for example: 5000 A considerable pressure drop may be encountered through the reactor bed at /hour, or 6,500 per hour. S 11 201245120 Although every mole of acid is miscellaneous, the production of mol-ethanol is actually the same as the molar ratio of the towel to the acid: from about 1〇〇:丄 to 1 · 100 ' From 50.1 to 1: 5〇, from 2〇: i to i: 2, or from 12: 1 to 1: Bu is best for the molar ratio of hydrogen to acetic acid greater than 2: for example: greater than or greater than 8 : 1. Time) is also a big difference, depending on the amount of acid, the 'catalyst' reaction, H' temperature and pressure, etc. Typical contact time ranges from less than 1 second's duty and above. If the catalyst system other than the fixed bed is used, the preferred contact time for the gas phase reaction is at least between αι and just seconds, for example: from 〇 3 to 80 seconds or 0, 4 to 30 seconds. The gasification of acetic acid to form ethanol is preferably carried out in the presence of a hydrogenation catalyst. Suitable hydrogenation catalysts include a species comprising a first metal of the first metal and (4) or a third metal of the third metal metal amount, optionally supported on the support of the lining. The first metal and the optional second metal and third metal may be selected from the group consisting of elements comprising the periodic table =, IIIB, IVB, VB, VIB, qing, or group transition metals, lanthanide metal fishing metals or Any metal from the group of the ancestors of the periodic table, IVA, VA, or VIA. Preferred metal combinations in some typical catalyst compositions are selected from the group consisting of chain/tin, turn/turn, chain/chain, palladium/ruthenium, palladium/ruthenium, cobalt/palladium, knot/ming, drill/complex, surface/shu, beginning / tin, silver / handle, copper / bismuth, copper f, record / handle, gold / handle, 钌 / 铼 and 钌 / iron. A typical catalyst is further described in U.S. Patent No. 4,608,744, and U.S. Patent Application Serial No. 2, the entire disclosure of which is incorporated herein by reference. In another embodiment, the catalyst is included in the type of catalyst. Blind is contained in the U.S. patent. Please disclose the case toilet/song lion, the entire contents of which are hereby incorporated by reference. In an embodiment, the catalyst comprises a first metal selected from the group consisting of copper, iron, start, record, = money,, "new" titanium, zinc, chromium, antimony, and tungsten. The first metal is selected from the group consisting of m and 钌. More preferably, the first metal is selected from the surface. In the embodiment of the present invention, when the first metal is the first, the second is the medium age of the catalyst. The amount is less than 5% by weight, such as less than 3% and 4% by weight of i. This is due to the high commercial demand for platinum. 12 201245120 As described above, in the embodiment, the lining also includes the second The metal, usually used as a promoter, if present, the second metal is preferably selected from the group consisting of copper, key, mmt'm, 钌, chain, gold, and town. More preferably The second metal is selected from the group consisting of copper, tin, and the like. More preferably, the second metal is selected from the group consisting of kicking and smashing. The weld bead, in some embodiments, includes two or more Metals such as first metal and second gold > 1, job-gold turnover can be (four) 丨 weight% to lG heavy autumn from αι weight in f weight%, or from 〇·ι refrequency 3wt%. The second metal is preferably used in an amount of from Gj% by weight to 20% by weight, for example from Q1% by weight to 1% by weight, or from 0.1% by weight to 5% by weight. For two or two types The above metal catalysts: IS various metals may be alloys with each other, or may include non-alloyed metals. Liquids may have slightly different metal ratios depending on the type of use. In the mode, the molar ratio of the first metal to the second metal == 10:1 to Π, for example, from 4:1 to 1:4, from 2:1 to 1: from 1 to 1: 1:5, or From 1.1 ·· 1 to 丨:u. 1 , the medium may also include a working metal 'the third metal may be selected from any first metal or second metal that is turned off' as long as the third metal is different from the first metal and the first In the preferred embodiment, the third metal is selected from the group consisting of a start, a pin, a nail, a copper, and a chain. The third metal is selected (four), and the staple is omitted. The total weight is from 0.05% by weight to 4% by weight, for example: from = to 3% by weight 'grade αι% by weight to 2% by weight. Dongli / = one or more kinds of metals, in this hair Some of the embodiments described above, "comprising a support stand ν branched or modified building body. The term "modification support body" used in this article - cut the financial domain of the voyage, finance _ ^ support the building body or change the f body (10) weight of the face ship weight 7 = heavy autumn, for example: from the % heavy Wei to 97% by weight, or from 8〇 重〇直直 I In the preferred solid way of using the modified body, the support modifier contains 9 amount 5 201245120 = total weight of the medium (u% to 5G) % by weight, for example: from Q 2% by weight to 25 weights 1/6 from G.5 to 15% by weight, or from 丨% by weight to 8% by weight. Catalyst = metal can be dispersed throughout the branch body, layered Formed throughout the baffle body, coated on the outer layer of the support (ie, 'egg shell"), or coated on the surface of the support. Those skilled in the art will be aware of the choice of the support material, The contact medium is economically active, selective and stable under process conditions for forming ethanol. Suitable support materials may include, for example, a stable metal oxide based support. Or shouting the support. The preferred domain includes the dragon, such as sulphur dioxide, yb shixi / oxidized Shao, sinensis Salts, such as sulphuric acid, pyrolysis of sulphur dioxide, high purity-oxygen cutting and mixtures thereof. Other readings may include, but secretly iron, oxidized, titanium dioxide, oxidized, oxidized, carbon , stone, ink, high surface area graphitized carbon, activated carbon, and mixtures thereof. As described above, the support of the catalyst may be modified with a support modifier. In some embodiments, the support modifier may be acidic. a modifier which increases the acidity of the catalyst. Suitable acidic support modifiers may be selected from the group consisting of metal oxides of Group IVB of the Periodic Table, metal oxides of the Periodic Table, metal oxides of Group VIB of the Periodic Table, Group VIIB of the Periodic Table. a group of metal oxides, metal oxides of Group VIIIB of the Periodic Table, oxidation, and mixtures thereof. Acidic bulk modifiers include those selected from the group consisting of Ή〇2, Zr〇2, Can 2〇5, Ta2〇 5, Ai2〇3, B2〇3'P2〇5, and a group consisting of Sb2〇3. Preferred acidic support modifiers include those selected from Ti〇2 'Zr〇2 'Nb2〇5, shame 5, and a group of Al2〇3. Acid modifiers may also include W 3, Mo〇3, Fe2〇3, Cr2〇3, V2〇5, _&, Cu〇, C〇2〇3, and Bi2〇3. In another embodiment, the support body is modified The agent may be a low volatility or non-volatile alkaline modifier. Such an alkaline modifier, for example, may be selected from (i) alkaline earth oxides, (11) metal oxides (iii) Alkaline earth metal bismuth citrate "iv;) alkali metal bismuth citrate, (v) periodic table lanthanide metal oxide, (vi) periodic table jjB metal bismuth citrate, (νΠ) periodic table lanthanide metal oxidation And (viii) a Group IIIB metal metasilicate, and a group of such compounds. In addition to oxides and metasilicates, it is also possible to use other modifications including nitrate, 14 201245120 varnish, helium salt and lactate. The acid-cutting agent is preferably a group consisting of an oxide selected from the group consisting of (IV), potassium, magnesium, and H-green zinc, and a mixture of any of the foregoing. More preferably, the oxime-selective modifier is Shi Xi _ ’ and the 纟 to the better is WeiliuasiQ3). For example, the secretory support modifier includes a partial lining, and preferably at least a part of the yaw gorge is in the form of crystal. The best cerium oxide support material is the ss6ii38 high surface of Saint-Gobain NorPro (hsa:>. This Saint_G〇bainN〇rPr〇SS611;38 oxidized Wei has the following properties: About % of the high surface area of the cerium dioxide surface area, force 250 square meters / gram, the median pore size measured by a mercury pore analyzer, the average pore volume is about L 〇 cubic centimeters / gram; and the bulk density (paddngden Qing) about 0.3S2 g/cm3 (η碎/cubic 呎). _ ^The preferred oxidized oxide/alumina support material is from Sud Chemie _(10) Dioxide Dream' has a nominal straight (four) 5 filaments, density About G 562 g / ml, the absorption is about 0.583 ^ g water / g of the building body, the surface area is about 16 〇 to 175 cf / g, and the pore volume is about 0.68 cc / g. The catalyst composition of the present invention is preferred In order to impregnate the modified building body with metal (_ (four) ah (four), but other processes, such as chemical vapor deposition v ah dep_〇n) can also be used. Such immersion technology is described in the US patent number , (10) and 7, 863, 489 and U.S. Patent Application Publication No. 2〇1_97485 , basins are included as a reference. ', especially 'saturated acid hydrogenation can achieve good acetic acid conversion rate and good ethanol selectivity ΐί rate 1 for the purpose of the present invention, "conversion rate" - the word refers to the acetic acid in the feed Conversion to the ratio of the t-forms prepared by 曰 1. The percentage of conversion of the fine pure towel Weimole is shown. The conversion rate can be at least just 'for example: at least, at least, to at least 6G%' At least 7 ()% or at least there is a battle. Although the blue media has a more embarrassing scale is desirable, such as at least 8G shouting at least 9 which, but in some embodiments ^ turn ethanol has a high selection of God, low job The conversion rate is acceptable. In many cases, it is easy to turn 'through the #_ circulation or make the Lai's reactor to make up the conversion rate, but it is more difficult to make up for the low selection rate. 15 201245120 The percentage of lion fine conversion acid County*. It should be recognized that each type of ~b compound has a social selection, and the lion rate and age rate are independent. For example, if the conversion of acetic acid to 6G mol% is converted to ethanol, the selectivity is 60%. Preferably, the chain soft door is known as ethanol. The selection rate is at least right m to the dereliction of duty, or to the twirling. The term i of the cap refers specifically to the compound ethanol 'acetaldehyde and ethyl acetate. The preferred rate of ethanol is 8 (U or more 'for example : at least 85% or at least 88%. Hydrogenation, such as, (10) and carbon dioxide have lower selectivity. The rate of selection of products that are not expected is better than 1%. More preferably, these are not detected. The expected product formation can be degraded 'and ideally less than 2%, less than 1%, or less than 0.5 per gram of vinegar converted to a ship, and the ship has little value other than as a fuel. - The term "yield," as used in ii, refers to the number of grams of product, such as ethanol, per kilogram of catalyst per hour during hydrogenation. Yield is produced per kilogram of hit county to > There is 1 gram of ethanol, for example, ······························································· The kilogram of catalyst produces 100 to 3, gram of ethanol per hour, for example, every kilogram of catalyst per hour to 2, then grams of ethanol or 6 (8) to 2 grams of ethanol per kilogram of catalyst per hour. The operation under conditions can result in at least 吨 1 ton per hour. Ethanol production 'eg at least i _ ethanol per hour, at least 5 ^ U per hour or at least 10 tons per hour ethanol production. Larger ethanol industry Production, depending on the scale, should generally be at least 1 whistling of ethanol per hour, for example: at least 15 collars of ethanol per hour or at least 30 tons of ethanol per hour 'in terms of range, large-scale ethanol industrial production' of the invention The process can produce from U to 160 tons of ethanol per hour, for example: Hour from 15 to 160 tons of ethanol or from 3 to 8 tons of ethanol per hour. From ethanol production by fermentation, due to the economic scale, ethanol is usually not allowed to be produced in a single facility, and ethanol production in a single facility can be borrowed. Obtained by using an embodiment of the present invention. In a different embodiment of the present invention, the crude ethanol product obtained by the hydrogenation process,
16 SI 201245120 的醋^任何1續加工，例如進行純化和分離之前^通常還包括未反應 括5曰重旦0乙醇和水。本文中所使用的術語“乙醇粗製品’“是指任何包 乙醇粗至7〇重量％的乙醇和5重量％至40重量％的水的組成物。 品典型的組份範圍例載於表i。表1中識別出之其他可以包 *例如·西^·法5 .%類、醚類、醛類、酮類、烷烴類，及二氧化碳。 r~—— -----------—., ----- ±1 · A? ^ Λ b .成分 一 乙醇 1 ·。畔租嚴而 濃度(重量 濃度(重量％) 濃度(重量％) 至 70 15 至 50 25 至 50 醋酸 ----_ 生____ 乙醛 -----J 0至50 15 至 70 20 至 70 LA_40 5至30 10 至 30 1〇 至 26 ϋ_3〇 0至20 1至12 3至1〇 〇_^_ιο___ 0至3 0.1 至 3 〇·2 至 2 0.1 至 6 0.1 至 4 — 在實知方式中’乙醇粗製品之醋酸可能含量為低於2〇重量％， 例如.低於15重量％，低於1〇重量％或低於5重魏。就範圍而言， f 1中之醋酸濃度範圍可由〇.1重量％至20重量％，例如：〇.2重量 %至15重量％，由〇.5重量％至10重量％或由1重量％至5重量％。 在具有較低量的醋酸的實施方式中，醋酸的轉化率較佳者為大於 、例如·大於85%或大於90%。此外，對乙醇的選擇率較佳也可 以為高的’以及較佳為大於75%，例如：大於85%或大於9〇〇/0。 乙醇的回收 根據本發明的實施方式之典型的乙醇回收系統係顯示於第丨圖和 第2圖中。系統1〇〇包括反應區1〇1和分離區1〇2。氫氣和醋酸分別 通過管路104和105供給到蒸發器no，在管路m中建立蒸氣進料 流並引到反應器103。在一實施方式中，管路1〇4和1〇5可以結合且 共同送入蒸發器110。在管路111内蒸汽進料流的溫度較佳為從1〇〇。€ 至350°C，例如：從12(TC至310°C，或150°C至300°C。任何不蒸 17 201245120 棄的3將上移出’如第1圖所示’以及可再循環或丟 ^ ηι …、罘1圖顯示管路in係引入反應器1〇3的頂部，但管 &丄i丄口J y入及施# . 1Π9 . _ μ心器103的側邊’上部或底部。反應區101和分離區 102之進―。步修改和附加元件如下所述。 實施103包含觸媒’表用於箏酸’較佳為醋酸，的氫化。在-•祕I·二# 張或多張保護床（未顯示）可以使用於反應器的上游， 俨泣bet發器U〇的上游，來保護觸媒免於接觸到在進料或返回/循 二1驗二之毋物或不良雜f。這樣的保護床可用在蒸氣或液體流。 It匕…床材料可以包括’例如：碳、二氧化石夕、氧化銘、陶兗， $ ^在—態樣中’保護床介質予以功能化(functionalized)，例如經 化的，用來捕獲特定的物種’如硫或㈣。在氫化製程中，較 :.、=斷地從反應胃1〇3經由管路112取出乙醇粗製品流。 + :路112中之乙醇粗製品流可冷凝並送到分離器1〇6，於是又提 供蒸氣流113和液體流m。適合的分離器⑽缺職塔或分液爸 (knockout pot)。分離器1〇6可以於從2(Γ(：至25〇。匚，例如：從扣 至225°C或6(TC至20(TC的溫度運作。分離器106的壓力可以從5〇 千帕至2000千帕，例如：從75千帕至1500千帕或從1〇〇千帕至1〇〇〇 千帕：隨意地，管路丨丨2中之乙醇粗製品可通經一種或更多種的膜來 分離氫氣及/或其他非可冷凝性氣體。 由分離器106逸出的蒸氣流Π3可包括氫氣及烴類化合物，其可 加以，除(purged)及/或送回到反應區1〇1。如所顯示的，蒸氣流ln、組 合以氫氣進料104且一起送入蒸發器11〇。在一些實施方式中，返回 的蒸氣流113可以在組合以氫氣進料1〇4之前予以壓縮。 從分離器106移出液體流114且系送到蒸顧塔1〇7的側邊。在一 實施方式中，液體流114之組成是與管路112中之從反應器所得到的 乙醇粗製品為實質上相似的，除了這些組成是已經耗乏了氫氣、二氧 化礙、甲烷及/或乙烷之外’較佳者為這些都被分離器1〇6所移除。於 是，液體流114也可稱為乙醇粗製品。液體流114之典型組成列於表 2中。應該理解到該液體流114可能包含其他未列出的成分，如從進 201245120 料所衍生的成分。16 SI 201245120 vinegar ^ Any 1 continuous processing, for example before purification and separation ^ usually also includes unreacted 5 曰 heavy denier 0 ethanol and water. The term "crude crude product" as used herein refers to any composition comprising ethanol in an amount of up to 7% by weight of ethanol and from 5% by weight to 40% by weight of water. Examples of typical component ranges are shown in Table i. Others identified in Table 1 may include *, for example, sm. 5, %, ethers, aldehydes, ketones, alkanes, and carbon dioxide. r~—— ------------., ----- ±1 · A? ^ Λ b. Ingredients One Ethanol 1 ·. Diffuse concentration and concentration (weight concentration (% by weight) concentration (% by weight) to 70 15 to 50 25 to 50 acetic acid----_ raw ____ acetaldehyde-----J 0 to 50 15 to 70 20 to 70 LA_40 5 to 30 10 to 30 1 to 26 ϋ _3 〇 0 to 20 1 to 12 3 to 1 〇〇 _ ^ _ _ _ _ _ 0 to 3 0.1 to 3 〇 · 2 to 2 0.1 to 6 0.1 to 4 — in a known manner The acetic acid content of the crude 'ethanol crude product may be less than 2% by weight, for example, less than 15% by weight, less than 1% by weight or less than 5. In terms of range, the concentration range of acetic acid in f 1 From 0.1% by weight to 20% by weight, for example: 〇.2% by weight to 15% by weight, from 5.5% by weight to 10% by weight or from 1% by weight to 5% by weight. In an embodiment, the conversion of acetic acid is preferably greater than, for example, greater than 85% or greater than 90%. Further, the selectivity to ethanol may preferably be high 'and preferably greater than 75%, for example: More than 85% or more than 9 〇〇 / 0. Recovery of Ethanol A typical ethanol recovery system according to an embodiment of the present invention is shown in the first and second figures. The reaction zone 1〇1 and the separation zone 1〇2 are included. Hydrogen and acetic acid are supplied to the evaporator no via lines 104 and 105, respectively, and a vapor feed stream is established in line m and directed to reactor 103. In one embodiment The tubes 1〇4 and 1〇5 can be combined and fed together into the evaporator 110. The temperature of the steam feed stream in the line 111 is preferably from 1 〇〇 to 350 ° C, for example: from 12 (TC to 310 ° C, or 150 ° C to 300 ° C. Any not steaming 17 201245120 discarded 3 will be removed from the 'as shown in Figure 1' and recyclable or lost ^ ηι ..., 罘 1 map display tube The road in is introduced into the top of the reactor 1〇3, but the tube &丄i丄 mouth J y enters and applies the side of the .1Π9 . _ μ heart 103 to the top or bottom. The reaction zone 101 and the separation zone 102 The step modification and additional components are as follows: Implementation 103 contains a catalyst 'table for the hydrogenation of zirconium acid', preferably acetic acid. In--- Secret I·2# or multiple guard beds (not shown) It can be used upstream of the reactor, weeping the upstream of the U-turn, to protect the catalyst from contact with the feed or return/test 2 or the miscellaneous f. The guard bed can be used in a vapor or liquid stream. It匕...the bed material can include 'for example: carbon, sulphur dioxide, sulphur, sputum, sputum, $ ^ in the state of 'protective bed media to be functionalized, For example, it is used to capture a specific species such as sulfur or (d). In the hydrogenation process, the crude ethanol product stream is withdrawn from the reaction stomach 1〇3 via line 112 in a hydrogenation process. + : The crude ethanol product stream in line 112 can be condensed and sent to separator 1 〇 6, thus providing vapor stream 113 and liquid stream m. A suitable separator (10) is a missing tower or a knockout pot. Separator 1〇6 can be operated from 2 (Γ(: to 25〇.匚, for example: from buckle to 225°C or 6 (TC to 20 (TC) temperature operation. The pressure of separator 106 can be from 5〇 kPa Up to 2000 kPa, for example: from 75 kPa to 1500 kPa or from 1 kPa to 1 kPa: Optionally, the crude ethanol in the line 可 2 can pass through one or more Membrane to separate hydrogen and/or other non-condensable gases. Vapor stream 3 escaping from separator 106 may include hydrogen and hydrocarbons which may be purged and/or returned to the reaction zone. 1 〇 1. As shown, the vapor stream ln, combined with the hydrogen feed 104 and fed together into the evaporator 11 〇. In some embodiments, the returned vapor stream 113 can be combined with a hydrogen feed of 1 〇 4 Compressed. The liquid stream 114 is removed from the separator 106 and sent to the side of the steam column 1〇7. In one embodiment, the composition of the liquid stream 114 is the ethanol obtained from the reactor in line 112. The crude product is substantially similar except that these compositions are already depleted of hydrogen, oxidizing, methane and/or ethane. These are all removed by the separator 1 〇 6. Thus, the liquid stream 114 can also be referred to as a crude ethanol product. The typical composition of the liquid stream 114 is listed in Table 2. It should be understood that the liquid stream 114 may contain other unlisted The ingredients, such as those derived from the 201245120 material.
在整财請書之表巾低於（<)_的量健者為林在，且如果 存在的話，僅可能存在微量，或存在大於〇〇〇〇1重量％。 1 2 其他賴”可以包括但不限於丙酸乙自旨、醋酸甲自旨、醋酸 異丙醋、醋酸正丙醋、醋酸丁酉旨或其混合物。表2中“其他嶋，，可以 包括但不祕⑽、f基乙細、異了基乙細或魏合物。表2中“立 他醇類”可能包括但不限於情、細醇、正鱗、正丁醇或其混合物、。 在:實施方式中’液體流114可包細醇，如異轉及/或正丙醇，其 含=從0.001至0.1重量％ ’從0 001至〇 〇5重量％或〇 〇〇1至〇 〇3 重量％。應該了解，這些其他成分可以繼續存在於這裡所述任何餾出 物或殘留物流内携帶之，在此不會進一步陳述，除非特別註明。 隨意地，管路.112中之乙醇粗製品或液體流114可以進一步送入 酯化反應器、氫解反應器或其等之組合。酯化反應器可以用於消耗掉 存在於乙醇粗製品内之醋酸以進—步減少待移除的醋酸的量。氫解可 以用於轉化乙醇粗製品内之醋酸乙酯成乙醇。 在第1圖所示的實施方式中，管路114引入第一蒸餾塔107之中 19 201245120 間部分，例如：四分之二或四分之三處。取決 品之組成及第一蒸顧塔107之操作條件，第叫内乙醇粗製 内之乙醇粗製品，較佳為不斷分離，一二J 107分離管路114 殘留物於管路116。管路117内之第H於管路1Π與第一 和其他重潑份，如果存在的話。在尤盆有至w未反應的醋酸'水， 高的醋酸轉化率之-些實施方式中，移除第 ^或至少90%之較 以及實質上全部的醋酸可能為有利的。 内报大部份的水 在約170千帕運作第一蒸鱗1〇7時 的溫度較佳為從90〇C至13〇〇c，例如.從9 &路116排出之殘留物 至說。由管路117排出之軸物的溫度較或從刚。C 例如：從65°c至85°c或挪至m：。在—^f 至90〇c， 館塔107壓力範圍可以從〇1千怕至5 方式巾’第-蒸 千帕或從1千帕至375千帕。 列如.從1千帕至475 如以上所討論的，管路117内夕楚& I , 之外還包含水。就細而言，f路117 = 和其他有機物 者為由4曰重秋至38罐，例如由7重量物^農度較佳 。如第1圖所示，在冷凝管路117内之第一二。物:ί 7 营路117内之第一顧出物係 ，之第德出物之别， 水分離器118可以為& 8以使第一顧出物脫水。 或其等之組合 種吸附早7^、臈、分子筛、萃取蒸娜單元， 中，水分離器118為一種壓變吸附(PSA)單元。 之溫度，影諸C至断 力下。壓變吸附罝_ 7、 千帕，例如··從1千帕至150千帕的壓 管路117之第輪凡0以包含2個床至5個床。水分離器118可以從 之95%的水’以及更佳為從水流⑽内 到第水。全糊份的水流⑽可返回 第—殘留物内。另外後由第—蒸祕】G7回收於管路116之 來、生&。#卜我擇一地，全部或部份的水流119可以經由管路 月、 餾出物117的剩餘部份離開水分離器118作為乙醇The amount of the towel in the whole book is lower than (<)_, and if it exists, only a trace amount may exist, or there may be more than 〇〇〇〇1% by weight. 1 2 Others may include, but are not limited to, propionic acid B, acetic acid, isopropyl acetate, n-propyl acetate, butyl acetate or mixtures thereof. Table 2, "Other defects, may include but not Secret (10), f-based, fine-formed or fine. The "sterols" in Table 2 may include, but are not limited to, alcohol, fine alcohol, n-butanol, n-butanol or mixtures thereof. In the embodiment: 'liquid stream 114 may comprise fine alcohol, such as iso- and/or n-propanol, which contains = from 0.001 to 0.1% by weight 'from 0 001 to 〇〇 5% by weight or 〇〇〇 1 to 〇 〇3% by weight. It should be understood that these other ingredients may continue to be carried in any of the distillates or residual streams described herein and will not be further described unless specifically noted. Optionally, the crude ethanol or liquid stream 114 in line 112 can be further fed to an esterification reactor, a hydrogenolysis reactor, or combinations thereof. The esterification reactor can be used to consume acetic acid present in the crude ethanol product to further reduce the amount of acetic acid to be removed. Hydrogenolysis can be used to convert ethyl acetate to ethanol in crude ethanol. In the embodiment shown in Fig. 1, the line 114 is introduced into the portion of the first distillation column 107 between 19 201245120, for example, two quarters or three quarters. Depending on the composition of the product and the operating conditions of the first steaming column 107, the crude ethanol product in the crude ethanol is preferably continuously separated, and the residue of the J 107 separation line 114 is in the line 116. The H in line 117 is in line 1 with the first and other heavy portions, if any. In some embodiments where the effluent has unreacted acetic acid 'water, high acetic acid conversion, it may be advantageous to remove the second or at least 90% of the substantially and substantially all of the acetic acid. It is reported that the temperature of most of the water running at the first steaming scale of about 170 kPa is preferably from 90 〇C to 13 〇〇c, for example, the residue discharged from the 9 & . The temperature of the shaft discharged from the line 117 is relatively high or constant. C For example: from 65°C to 85°c or to m:. In the range from -^f to 90〇c, the tower 107 pressure range can range from 〇1 to 5 ways to the first steamed kPa or from 1 kPa to 375 kPa. For example, from 1 kPa to 475, as discussed above, the conduit 117 contains water in addition to I and I. In detail, f road 117 = and other organic matter are from 4 曰 to 38 cans, for example, 7 weights are better. As shown in Figure 1, the first two in the condensing line 117. The water separator 118 may be & 8 to dehydrate the first product. The water separator 118 is a pressure swing adsorption (PSA) unit, or a combination thereof, which adsorbs the early 7^, hydrazine, molecular sieve, and extraction steaming unit. The temperature is affected by C to the breaking force. Pressure swing adsorption 罝 _ 7, kPa, for example, from 1 kPa to 150 kPa, the first round of the pressure line 117 is 0 to contain 2 beds to 5 beds. The water separator 118 can be from 95% of the water' and more preferably from the water stream (10) to the first water. The full paste water stream (10) can be returned to the first residue. In addition, it is recovered by the first steaming G7 in the pipeline 116, raw & Alternatively, all or part of the water stream 119 can exit the water separator 118 as ethanol via the pipeline month and the remainder of the distillate 117.
S 20 201245120 混合物流120。管路1〇8之第一 著階段的數1G ° 可能會ί 女於士 胁效率及/或饋料組成而有所不同。以 n 比操作可能係較欠佳，因為可能需要更多能量來操作 第二讀塔1G7 〇較佳者為，乙_合物流12 反号 在顯7F於第1圖中之另—態樣巾，水流119内全部或部份的水係 在=路108之該第-顧出物回流到第一蒸館塔1〇7的位置下方之 至第一蒸餾塔107。 貝 笞路116之乙醇思合物流12〇和第—殘留物之典型成分係提供於 下面表3中。應該理解的是’此等物流還可能包含未列出的其他成分， 如從進料所衍生的成分。 表3 :具PSA之第一蒎潑技 濃度(重詈°/〇) 濃度(重量％) 濃度(重量％) 乙醇混合物流 乙醇 20 至 95 30 至 95 40 至 95 水 <10 0.01 至 6 0.1 至 2 醋酸 < 2 0.001 至 0.5 0.01 至 0.2 醋酸乙酯 <60 1至55 5至55 乙醛 <10 0.001 至 5 0.01 至 4 縮醛 <0.1 <0.1 < 0.05 丙嗣 <0.05 0.001 至 0.03 0.01 至 0.025 殘留物 醋酸 <90 1至50 2至35 水 3〇 至 1〇〇 45 至 95 如至90 乙醇 <1 <0.9 <0.3 一些物種，如縮醛類，可能在第一蒸餾塔1〇7中分解以至於餾出 21 201245120 物或殘留物域留非常低量或甚至檢測不到的量之縮_ ^外，在 乙酵粗製品離開反應器103之後，乙醇粗製品内可能出現醋酸與乙醇 之間以及醋酸乙g旨與水之騎平衡反應。取決於乙醇粗製品内之醋酸 的濃度’此平衡可__向形觸紅i此平衡可峨用乙醇粗 製品的滯留時間及/或溫度來調節。 取决於第-蒸館塔1〇7的殘留物内所含的水與醋酸之量，管路以 可以於-誠多種下列的製程來處理。下列為進—步處理第一殘留物 =典型的製程，且賴了解到可以使用下狀任-者，而不論酷酸的 /辰度為何冨殘留物含有大部份的醋酸時，例如，大於7〇重量％，殘 留物可以循環至該反應器而不需任何水之分離。在一個實施方式中， 當殘留物含有大部份的魏時，例如，大於5Q重量％，殘留物可以分 ，成醋酸流及水^ _在，實施方式巾也可峨具有較低的醋酸 濃度之第一殘留物來回收。殘留物也可以藉纟蒸顧塔或-種或多種膜 而分離成醋酸及水流。設若使用—種膜或陣列膜组來分離醋酸和水， 膜或陣列臈組可以選自於賴移除滲透水流之任何適合的耐酸膜。所 產生的醋贿選擇性地返回至反顧1Q3。所產生的水流可以使用作 為萃取劑，例如如以下所討論之經由管路121至第二蒗 來水解-種含賴於水解單元。 ‘''^1〇9戈 在其他實施方式中，舉例而言，在管路116的第一殘留物含有低 ，咒重量％的醋酸處’可能的選擇包括以下的一者或多者：⑴使一 5伤的殘留物返回至反應g⑽，⑼巾和醋酸，㈣使醋酸與醇反應， f(IV)到廢水處理設施來處理殘留物。使用弱酸回收(WAR)蒸餾塔來 分離含有低於50重量％的醋酸之殘留物也是可能的，可添加溶劑(選 擇性地作用為一種共沸劑)至該弱酸回收蒸餾塔。可能適合本目的之典 型=溶劑包括醋酸乙酯、醋酸丙酯、醋酸異丙酯、醋酸丁酯、醋酸乙 烯酯二二異丙醚、二硫化碳、四氫呋喃、異丙醇、乙醇，及c3_Ci2烷 烴。當中和醋酸時，較佳者為管路110的殘留物含有低於1〇重量％的 醋騃。醋酸可以用任何適合的鹼金屬氧化物基料或鹼土金屬氧化物基 料，例如：氫氧化鈉或氫氧化鉀。當使醋酸與醇反應時，較佳者為$ 22 201245120 留物含有低於50重量％的醋酸。醇可以為任何適合的醇，例如：曱醇、 乙醇、丙醇、丁醇，或其等之混合物。該反應形成酯，其可和苴他系 統整合，例如：羰化生產或酯生產製程。較佳地，醇含有乙醇^及所 產生的酯含有醋酸乙酯。選擇性地，所產生的酯可送至氫化反應器。 於-些實施方式中，當第-殘留物含料少量的醋酸時，& : 低於5重量％，殘留物可以不需進—步處理而到廢水處理設施 理。殘留物之有機的内含物，例如醋酸内含物，可有益地適合於用來 餵養廢水處理設施所使用之微生物。 一回到第1圖巾，乙醇混合物流120引到第二蒸德塔咖，也稱為" 輕顧份蒸條” ’較佳者為引到蒸鶴塔109之頂部部分，如頂部二分之 -或頂部二分之-處。第二蒸餾塔109可為塔盤蒸館塔或填充基顧 塔。在一實施方式中，第二蒸餾塔109是塔盤蒸餾塔，具有5至70(個） 塔盤，例如：從15至50(個)塔盤或從20至45(個)塔盤。舉一個例子， 當沒有利用水萃取時，蒸娜制3G塔盤_塔，則 120引入塔盤2。 、選擇性地’ _份_塔可能是—種萃取_塔。合適的萃取劑 可以包括二曱_、甘油、二伸乙甘醇、L萘紛、氫酿、取，、二甲 基曱醯胺1，4_了_醇，乙二醇.^戊：醇；丙二醇四甘醇.聚乙二醇； 甘油丙二醇-四甘醇_Μ·丁二醇、乙醚、甲酸甲醋、環己烧、耶匕二 曱基-1，3_丙二胺、甲基乙二胺、二伸乙三胺、己二胺幻3_二 胺基戍炫、-觀基化齡、十冰、十球、十诚、氯化石峨， 或其等之組合。在另-態樣巾，萃取劑可以是包括水的含水流。如果 萃取劑包水，則水可從外部來源或n衫座其他驗塔從内部 =收/循環&路而得之’例如水流119。__般而言，萃取劑可以送入乙 醇混合物流120的入口點上方’如同由選擇性的管路121所顯示。當 使用萃取糾，可以制合適的回收祕，例如另外的蒸鱗，來移 除皁取劑，且如有需要便使用來循環萃取劑。 第二蒸顧塔109係被用來分離乙醇混合物流12G或其之-部分成 為管路123内的第二德出物和管路122内的第二殘留物。管路123内 r； 23 201245120 Ϊ第，财乙轉⑽，料二_物包含乙 雜地為可供销售的完成的乙醇產品。 千括至^千—帕的溫度和壓力可能會有所變化，當在大約2〇 75°C，例如··從U排出的第二殘留物之溫度較佳為3(TC至 之管路123排出的第二或從价至65°C。在第二蒸娜1〇9 抑至5(rc或從…至^溫，佳為2(TC至55。〇：，例如·.從 操作，接近真空條件或於直:第—_塔可在降低_力下 之分離j其它實施;;1件’以進—步有利於醋酸乙g旨與乙醇 帕至510千帕，例如.二’第二蒸鱗109之壓力範圍可從0.1千 第二蒸鱗109之典_ ^至475千帕或從1千帕至375千帕。 理解的是，第二餘出物和^=殘留物組成物列於下面表4中。應該 如在進料中喊分。 殘留物還可能包含其他未列出的成分，S 20 201245120 Mixture stream 120. The number 1G ° of the first stage of the line 1〇8 may vary depending on the efficiency and/or composition of the feed. Operation with n ratio may be less desirable, as more energy may be required to operate the second read column 1G7. Preferably, the B-combination flow 12 is in the form of a different sample in Figure 1F. All or part of the water in the water stream 119 is returned to the first distillation column 107 at a position below which the first-out product of the =108 is returned to the first vaporization column 1〇7. The typical composition of the ethanol hydration stream 12 〇 and the first residue of the Bayer Road 116 is provided in Table 3 below. It should be understood that 'these streams may also contain other ingredients not listed, such as ingredients derived from the feed. Table 3: First 蒎 splash concentration with PSA (weight 詈 ° / 〇) Concentration (% by weight) Concentration (% by weight) Ethanol mixture flow ethanol 20 to 95 30 to 95 40 to 95 water < 10 0.01 to 6 0.1 To 2 acetic acid < 2 0.001 to 0.5 0.01 to 0.2 ethyl acetate < 60 1 to 55 5 to 55 acetaldehyde < 10 0.001 to 5 0.01 to 4 acetal < 0.1 < 0.1 < 0.05 < 0.05 嗣 < 0.05 0.001 to 0.03 0.01 to 0.025 Residual acetic acid <90 1 to 50 2 to 35 Water 3〇 to 1〇〇45 to 95 as to 90 Ethyl alcohol <1 <0.9 <0.3 Some species, such as acetals, It is possible to decompose in the first distillation column 1〇7 so that the distillate 21 201245120 or the residue domain remains in a very low amount or even an undetectable amount, after the crude ethyl acetate leaves the reactor 103, There may be an equilibrium reaction between acetic acid and ethanol and acetic acid in the crude ethanol product. Depending on the concentration of acetic acid in the crude ethanol product, this balance can be adjusted by the residence time and/or temperature of the crude ethanol product. Depending on the amount of water and acetic acid contained in the residue of the first steaming tower 1〇7, the piping can be processed in various processes as follows. The following is the first step of the first residue = typical process, and it is known that the following can be used, regardless of the acidity/length of the acid, the residue contains most of the acetic acid, for example, greater than At 7% by weight, the residue can be recycled to the reactor without any separation of water. In one embodiment, when the residue contains most of the Wei, for example, more than 5Q% by weight, the residue can be divided into acetic acid stream and water. In the embodiment, the towel can also have a lower acetic acid concentration. The first residue is recovered. The residue can also be separated into acetic acid and water by means of a steaming tower or a membrane or membranes. If a membrane or array of membranes is used to separate the acetic acid and water, the membrane or array of tantalum can be selected from any suitable acid resistant membrane that removes the permeate stream. The resulting vinegar bribes are selectively returned to turn back to 1Q3. The resulting water stream can be used as an extractant, for example, hydrolyzed via line 121 to second enthalpy as discussed below, depending on the hydrolysis unit. In other embodiments, for example, the first residue in line 116 contains a low, cursed weight of acetic acid. The possible choices include one or more of the following: (1) Return a 5 wound residue to the reaction g (10), (9) towel and acetic acid, (4) react acetic acid with the alcohol, and f (IV) to the wastewater treatment facility to treat the residue. It is also possible to separate a residue containing less than 50% by weight of acetic acid using a weak acid recovery (WAR) distillation column to which a solvent (optionally acting as an azeotropic agent) can be added to the weak acid recovery distillation column. Typical values that may be suitable for this purpose = Solvents include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, vinyl acetate diisopropyl ether, carbon disulfide, tetrahydrofuran, isopropanol, ethanol, and c3_Ci2 alkanes. When neutralizing acetic acid, it is preferred that the residue of line 110 contain less than 1% by weight of vinegar. The acetic acid may be any suitable alkali metal oxide base or alkaline earth metal oxide base such as sodium hydroxide or potassium hydroxide. When acetic acid is reacted with an alcohol, it is preferred that the residue is $22 201245120 and the residue contains less than 50% by weight of acetic acid. The alcohol can be any suitable alcohol, such as decyl alcohol, ethanol, propanol, butanol, or mixtures thereof. The reaction forms an ester which is compatible with the other systems, such as a carbonylation or ester production process. Preferably, the alcohol contains ethanol and the ester produced contains ethyl acetate. Alternatively, the ester produced can be sent to a hydrogenation reactor. In some embodiments, when the first residue contains a small amount of acetic acid, & : less than 5% by weight, the residue can be passed to the wastewater treatment facility without further processing. The organic content of the residue, such as the acetate content, can be advantageously adapted to the microorganisms used to feed the wastewater treatment facility. Upon returning to the first towel, the ethanol mixture stream 120 is directed to the second steamed Deta coffee, also known as "Looking at the steamed strips." Preferably, the top portion of the steamed crane tower 109 is introduced, such as the top two points. The second distillation column 109 may be a tray vaporization column or a packed base column. In one embodiment, the second distillation column 109 is a tray distillation column having 5 to 70 Tray, for example: from 15 to 50 trays or from 20 to 45 trays. As an example, when no water extraction is used, steaming the 3G tray _ tower, then 120 is introduced into the tower Disk 2. Selectively ' _ _ _ tower may be - an extraction _ tower. Suitable extractants may include diterpene _, glycerol, diethylene glycol, L-naphthalene, hydrogen, take, dimethyl Base amide 1,4_ _ alcohol, ethylene glycol, pentane: alcohol; propylene glycol tetraethylene glycol. polyethylene glycol; glycerol propylene glycol - tetraethylene glycol Μ 丁 butyl diol, diethyl ether, methyl formate, Cyclohexene, yttrium dimercapto-1,3_propylenediamine, methylethylenediamine, diethylenetriamine, hexamethylenediamine, dioxin-3,diamine, fluorene, guanine age, ten ice , ten balls, ten since, chlorinated stone, or In the case of the other sample, the extracting agent may be an aqueous stream comprising water. If the extracting agent is water-containing, the water may be obtained from an external source or a n-seat other tower from the internal = receiving / recycling & For example, water stream 119. __ In general, the extractant can be fed above the entry point of the ethanol mixture stream 120 as shown by the optional line 121. When using extraction correction, a suitable recovery can be made, for example An additional steaming scale is used to remove the soap extractant and, if desired, to recycle the extractant. The second steaming tower 109 is used to separate the ethanol mixture stream 12G or a portion thereof into the conduit 123. The second residue in the second German product and the pipeline 122. The pipeline 123 is in the r; 23 201245120 Ϊ第, 财乙转(10), the material _ contains the mixed product for the completed ethanol product for sale. The temperature and pressure may vary from 0 to 75 ° C. When the temperature is about 2 to 75 ° C, for example, the temperature of the second residue discharged from U is preferably 3 (TC to line 123 is discharged). The second or ad valorem to 65 ° C. In the second steaming 1〇9 to 5 (rc or from ... to ^ temperature, good 2 (TC to 55) 〇:, for example, from operation, close to vacuum conditions or in straight: the first - _ tower can be separated under the _ force j other implementation;; one piece of 'steps' favors the acetic acid The pressure range up to 510 kPa, for example, the second 'second steaming scale 109 can range from 0.1 thousand to the second steaming scale 109 to 475 kPa or from 1 kPa to 375 kPa. Understand that the second The remainder and ^=residue composition are listed in Table 4 below. It should be shouted as if it were in the feed. The residue may also contain other unlisted ingredients.
S 201245120 較佳者為低於〇 4 : 1，如：低於〇 2 : 1或低於〇.i : 1。 管路123内之第二餾出物，其包括醋酸乙酯及/或乙醛，較佳者為 如第1圖所示加以回流，例如：其回流比從丨：30至3〇 :丨，例如： ^ 1 . 1.5至15 . 1或從1 : 5至5 : 1。在一態樣中，管路123内之第 二餾出物或其之部份可能送回反應器1〇3。舉例來說，使部分的第二 ，出物123返回至反應器103可能為有利的。第二餾出物内之醋酸乙 酯及/或乙醛可以於氫化反應器1〇3或於第二反應器中進一步反應。由 第二反應器之流出物也可以送至反應器103以生產額外的乙醇或至一 蒸顧塔，例如：蒸餾塔107、115，或118，來回故額外的乙醇。 在顯不於第1圖之實施方式中，藉由本發明的製程所生產的完成 的乙醇產品可以從管路122的第二殘留物取得。完成的乙醇產品有利 地可依據本發明使用水分離器或2個蒸餾塔來回收之。完成的乙醇產 品可以為工業級乙醇，其包括從75至96重量％之乙醇，例如：從8〇 ，96重量％，或85至96重量％之乙醇，該百分率係以乙醇產品總重 量為基準。典型完成的乙醇成分範圍如下表5所列。 _________ 表5 :完成的乙醇組成物 成分 濃度(重量％) 濃度(重量％) 濃度(重詈 乙醇 '~~ 75 至 96 80 至 96 85 至 96 水 <12 1至9 3至8 醋酸 <1 <0.1 <0.01 醋酸乙酯 <2 <0.5 <0.05 縮醛 <0.05 <0.01 < 0.005 丙_ <0.05 <0.01 < 0.005 異丙醇 <0.5 <0.1 <0.05 正丙醇 <0.5 <0.1 <0.05 本發明之完成的乙醇組成物較佳為含有非常低量，例如：低於〇 5 重量％，之其他醇類，如曱醇、丁醇、異丁醇、異戊醇及其他c4_C2〇S 201245120 is preferably lower than 〇 4 : 1, such as: lower than 〇 2 : 1 or lower than 〇.i : 1. a second distillate in line 123 comprising ethyl acetate and/or acetaldehyde, preferably refluxed as shown in Figure 1, for example, having a reflux ratio from 丨: 30 to 3 〇: 丨, For example: ^ 1. 1.5 to 15.1 or from 1: 5 to 5: 1. In one aspect, the second distillate in line 123 or a portion thereof may be returned to reactor 1〇3. For example, it may be advantageous to return a portion of the second, exit 123 to the reactor 103. The ethyl acetate and/or acetaldehyde in the second distillate may be further reacted in the hydrogenation reactor 1〇3 or in the second reactor. The effluent from the second reactor can also be sent to reactor 103 to produce additional ethanol or to a distillation column, such as distillation column 107, 115, or 118, to recycle additional ethanol. In an embodiment that is not shown in Figure 1, the finished ethanol product produced by the process of the present invention can be taken from the second residue of line 122. The finished ethanol product can advantageously be recovered in accordance with the present invention using a water separator or two distillation columns. The finished ethanol product may be a technical grade ethanol comprising from 75 to 96% by weight of ethanol, for example from 8 〇, 96% by weight, or 85 to 96% by weight of ethanol, based on the total weight of the ethanol product. . Typical ranges of ethanol components are listed in Table 5 below. _________ Table 5: Concentration of finished ethanol composition (% by weight) Concentration (% by weight) Concentration (repeated ethanol '~~ 75 to 96 80 to 96 85 to 96 water < 12 1 to 9 3 to 8 acetic acid < 1 < 0.1 < 0.01 ethyl acetate < 2 < 0.5 < 0.05 acetal < 0.05 < 0.01 < 0.005 propylene < 0.05 < 0.01 < 0.005 isopropyl alcohol < 0.5 < 0.1 <0.05 n-propanol <0.5 <0.1 <0.05 The finished ethanol composition of the present invention preferably contains a very low amount, for example, less than 5% by weight, and other alcohols such as decyl alcohol and butyl Alcohol, isobutanol, isoamyl alcohol and other c4_C2〇
Cl· 25 201245120 醇。在一實施方式中’在完成的乙醇組成物中之異丙醇含量從8〇至 1，000重量ppm ’例如：從95至1〇〇〇重量ppm，從1〇〇至700重量 PPm或從150至5〇〇重量ppm。在一實施方式中，完成的乙醇組成 物較佳為貫質上不含乙醛，並選擇性包括低於8重量ppm，如低於5 重里ppm ’或低於1重量之乙藤。 在一些實施方式中，當使用進一步的水分離時，乙醇產品可以由 以上討論的水分離單元取出為物流。在此等實施方式中，乙醇產品的 乙醇濃度可能比表5中表示的更高，以及較佳者為大於97重量％的乙 醇’例如：大於98重量。/。或大於99.5重量％的乙醇。此態樣中之乙 醇產品較佳者為包括低於3重量％的水，例如：低於2重量％或低於 〇.5重量％的水。 在本發明另一實施方式中，如第2圖所示，來自第一蒸餾塔之管 路in内第一餾出物通經壓縮器13〇以及饋至膜131。膜131較佳可 以在氣相下操作。管路117内之第一餾出物的水滲透穿過膜131來形 成滲透物流132。滲透物流Π2可包含來自該第一餾出物之至少80〇/〇 $水’以及更佳為至少90%的水。在一實施方式中，滲透物流132亦 含有來自該第一餾出物之低於10%的乙醇，例如，低於5%的乙醇。 一部份的滲透物流132可返回到第一蒸餾塔1〇7，較佳於液體流114 的進料處下方。-部份的滲透物流132可以如所顯示的經由管路133 而從系統被清除’來控制第一蒸餾塔1〇7内之水量。 未透過膜131之部份的餾出物則係形成滯留物流(retentate s=am)134 ’勤是乙醇混合物流’且如上第丨圖巾所綱的係饋至第 二蒸顧塔109。在-實施方式中，滞留物、流134包含有比提供於表3 内之乙醇混合物流組成更多的水。舉例而言，滯留物流m可包含由 0至ίο重里％的水’以及更佳者為由0至5重量％的水。滯留物流134 t存在之額外的水可能有利於分離第二蒸鶴塔109 Θ之醋酸乙酿和乙 醇。饋至第二蒸館塔109之額外的水較佳者為用管路122内的第二殘 留物來移除，以及如以上討論的’可能需要二次的脫水步驟以提供具 有所想望的水濃度之乙醇產品。 ~ 26 201245120 雖然於第2圖中只顯示一膜，但應該了解到亦可以使用合適的陣 列膜組。 在本發明多數的實施方式中，希望達成如第1圖和第2圖所示的 由第―餾出物來移除水。於第3圖中，管路117内之第一餾出物分流 成主管路14〇與旁通管14卜在一實施方式中，分流比可以為由ι〇:ι 至1:10的範圍，例如由5:1至1:5或約1:1。主管路140係饋至水分離 器U8來生產水流142和乙醇混合物流143。水流142可如上第i圖 和第2圖中所說明之返回到第一蒸餾塔107。管路117内部份的第一 餾出物可冷凝以及經由管路1〇8回流到第一蒸餾塔1〇7，例如，回流 比從10:1至1:1〇〇 ’例如由2:1至1:5〇或由1:1至1:1〇。旁通管⑷ 可由回流管路108取得以及和乙醇混合物流143 一起直接饋至第二蒸 ，塔109。可以使用流量控制閥(未顯示於此)來控制主管路140與旁通 管Ml之間的分流以使得希望的水濃度饋至第二蒸顧塔1〇9。在—未 顯示的實施方式巾，—部份齡通管141 _流到第-麵塔1〇7。 在另-實施方式中’旁通管141不回流到第—蒸餾塔1G7，且可以有 士獨立分開的回流管路（未顯示於此旁通管⑷的一部份可以被冷 ^9且可與全部或部份的乙醇混合物流143分別地饋人至第二蒸餘^ 可以基於主执14G與赖f⑷雜合之物流巾 度來控-館出物117之分離，將其分離成主管路14〇與 在實施方式中，旁通管141含有比乙醇混合物流143更高的4 =又:組合，出物與乙醇混合物具有大於心机％的總水濃度，合 於2 wt.%或大於5 Μ %。就範圍而言，組 5 為由〇·5至15…如由2至㈣;Ϊ: 5至1 〇 wt.%〇旁通管141肉沾 > 人θ 内之乙醇^麟有觀分轉二細塔抑 在另—實施方式中，額外的水可以經由管路⑵ 而添加至第二蒸餾塔1〇9。遝摆^丄 至蒸娜U)9。 選擇性地，可以添加水流142内部份的冲 "s巾所不之各個讀塔，其可選自於任何㈣執行特定 27 201245120 的分離及/或純化步驟之蒸餾塔。較佳者為各個 塔:其具有⑴50個塔盤，例如：由1〇至⑽個塔^^盤^ 個塔盤或由30至75個塔盤。塔盤可為餘盤，固定關 盤’或具有本技藝已知的任何其計固塔 絲娜。_域娜μ ,規_4^^=可 使用。&私盤或赫可安置於—連續的蒸館塔，或者1等可能安 在兩座或更多座的蒸娜，其可使得統從第—座進人第二座 體從第二座進入第一座等等。 液 為方便起見，第-論塔_出物和_物也可稱為 物二或“第-殘留物，，。其他蒸顧塔的館出物或殘留物也可具有類似 =修，語(第二’第三等），以區分彼此，但這樣的修倚語不應被解 釋為要求任何特定的分離順序。 配用於每-蒸德塔的相關冷凝器和液體分離槽可以是任何傳統的 設=、’並簡化於圖式中。熱量可以提供給每個蒸顧塔底部或使底部流 循％通過熱交換H或再騎。也可賴其他_的再㈣，如内部再 沸器。提供再沸器的熱量可來自任何製程中所生成的熱量，該製程可 和再沸器整合或配射卜部麵，如其他產生熱的化學製程或鋼爐。雖 然如圖式情示只具-反應師—閃蒸塔，但是在—些本發明實施方 式中可以細加的反應H、閃蒸塔、冷絲、加熱元件和其他元件。 對此領域之熟悉技藝者即知通常用來進行化學製程之各種冷凝器、 泵、壓縮機、再沸器、轉筒、閥門、連接器、分離容器等，也可進行 合併’並用於本發明的製程中。 用於蒸館塔的溫度和壓力可能會有所不同。就實際問題而言，雖 然在-些實施方射可贿耻魏勤（subatmQspheriepres_s) 或超大氣壓力，但在這些區域中一般會用的壓力從10千帕至3000千 帕。不同區域内的溫度一般介於移除之餾出物組成物和移除之殘留物 組成物的沸點之間。對此領域之熟悉技藝者即知在運作蒸餾塔内某一 點的溫度是依賴於在該位置的物料組成和蒸潑塔壓力。此外，視生產 製程的規模而定，進料速率可能會有所不同，且如果加以描述的話， 28 201245120 可能籠統地以進料重量比率表示。 本發明實施方式所生產之完乙醇組成物可適合制在多種應 、_、化工原料、藥品、清潔劑、消毒劑、燃氣遲輸 ϋ ’費。在燃料應用，完成的乙醇組成物可與汽油混合用於機動 ，載工具，如汽車、船隻和小型活塞式發動機飛機。在義料應用上， 完成的乙醇組成物可用作化妝品和美容製劑之溶劑、洗務劑、消毒劑、 ，料、油墨、和藥品。完成的乙軌成物還可以用作製程溶劑，供醫 藥產。σ，食品製劑，染料，光化學和乳膠加工之製造製程用。 凡成的乙醇組成物還可以用作化學原料來製造其他化學材料如 =、丙_乙0旨、醋酸乙_、乙稀、乙二_、乙胺、麵，及高碳 醇三尤其是丁醇。在生產醋酸乙s旨中，完成的乙醇組成物可藉由贈酸 進仃酉旨化。於另-應用，完成的乙醇組成物可脫水生產乙稀。任 知的脫水觸可簡來使乙醇脫水，如描述於朗憎翻專利 公開案號2010/0030002和2010/0030001 t，其等之全部内容及揭露在 此、·内入作為參考。彿石觸，舉例而言，可使用作為脫搞媒。較佳 為’沸石具有孔隙直徑至少約〇.6奈米，且較佳滞石包括脫水觸媒， 選自由絲光沸石’ ZSM-5 ’ ;’弗石X和沸石γ所組成之群組^沸石X， 舉例而言’描述於制專利第2,882,244號以及沸石γ描述於 利第3，DO,0〇7號’其等之全部内容在此納人作為參考。 為了使本文所揭露之本發明更有效地理解，下面提供實施例。應 該了解此等實施例只是舉舰明，而且無論如何不舰轉為限 發明。 【實施方式】 實施例 下面的實施例係用 料組成物及分離系統。 ASPENP1US 7」模擬軟體來製備以測試各種進 29 201245120 實施例1 包括56重量％的乙醇’ 38重量％的水，2重量。/〇醋酸乙g旨，2重 量％的乙醛’ 1重量％的醋酸，以及丨重量％其他的有機物之反應產物 以10磅每小時饋入1個蒸餾塔。蒸餾塔以5〇塔盤在大氣壓力下運作。 進料塔盤座落於從頂部之第35個塔盤。表6比較2個不同運作之德出 =成。於運作A每噸精^乙醇之能量需求大於運作b約5倍。Cl· 25 201245120 Alcohol. In one embodiment 'the isopropanol content in the finished ethanol composition is from 8 Torr to 1,000 ppm by weight', for example: from 95 to 1 〇〇〇 ppm by weight, from 1 700 to 700 重量 ppm or from 150 to 5 inches by weight ppm. In one embodiment, the finished ethanol composition preferably contains no acetaldehyde per pass and optionally comprises less than 8 ppm by weight, such as less than 5 ppm by weight or less than 1 weight of ethyl vine. In some embodiments, when further water separation is used, the ethanol product can be taken up as a stream from the water separation unit discussed above. In such embodiments, the ethanol product may have a higher ethanol concentration than that indicated in Table 5, and preferably greater than 97% by weight of ethanol', e.g., greater than 98 weight. /. Or greater than 99.5% by weight of ethanol. Preferably, the ethanol product in this aspect comprises less than 3% by weight water, for example less than 2% by weight or less than 5% by weight of water. In another embodiment of the present invention, as shown in Fig. 2, the first distillate in the pipe in from the first distillation column passes through the compressor 13 and is fed to the membrane 131. Membrane 131 is preferably operable in the gas phase. Water from the first distillate in line 117 permeates through membrane 131 to form permeate stream 132. The permeate stream 2 may comprise at least 80 〇 / 〇 $ water' and more preferably at least 90% water from the first distillate. In one embodiment, the permeate stream 132 also contains less than 10% ethanol from the first distillate, for example, less than 5% ethanol. A portion of the permeate stream 132 can be returned to the first distillation column 1〇7, preferably below the feed to the liquid stream 114. - Part of the permeate stream 132 can be purged from the system via line 133 as shown to control the amount of water in the first distillation column 1〇7. The distillate which is not permeable to the portion of the membrane 131 forms a retentate s = am 134 ', which is an ethanol mixture stream' and is fed to the second steam column 109 as outlined above. In an embodiment, the retentate, stream 134 comprises more water than the ethanol mixture stream provided in Table 3. For example, the retentate stream m may comprise from 0 to 3% by weight of water' and more preferably from 0 to 5% by weight of water. The additional water present in the retentate stream 134t may facilitate separation of the second steamed crane tower 109 from acetic acid and ethanol. The additional water fed to the second steaming tower 109 is preferably removed with a second residue in line 122, and as may be required for a secondary dewatering step as discussed above to provide the desired water. Concentration of ethanol products. ~ 26 201245120 Although only one film is shown in Figure 2, it should be understood that a suitable array of arrays can also be used. In most embodiments of the present invention, it is desirable to achieve the removal of water from the first "distillate" as shown in Figures 1 and 2. In FIG. 3, the first distillate in the line 117 is branched into the main line 14 and the bypass tube. In an embodiment, the split ratio may be in the range of ι:1 to 1:10. For example, from 5:1 to 1:5 or about 1:1. Main line 140 is fed to water separator U8 to produce water stream 142 and ethanol mixture stream 143. The water stream 142 can be returned to the first distillation column 107 as illustrated in Figures i and 2 above. The first distillate of the internal portion of line 117 can be condensed and refluxed via line 1〇8 to first distillation column 1〇7, for example, a reflux ratio of from 10:1 to 1:1〇〇, for example, by 2: 1 to 1:5〇 or from 1:1 to 1:1. The bypass line (4) can be taken from the return line 108 and fed directly to the second steam, column 109, together with the ethanol mixture stream 143. A flow control valve (not shown) may be used to control the split between the main line 140 and the bypass line M1 to feed the desired water concentration to the second steam column 1〇9. In the embodiment towel not shown, the partial passage pipe 141 _ flows to the first-side tower 1〇7. In another embodiment, the bypass pipe 141 does not flow back to the first distillation column 1G7, and may be separately separated from the return line (a part of the bypass pipe (4) not shown may be cooled and And all or part of the ethanol mixture stream 143 is separately fed to the second steaming room. ^ The separation of the library material 117 can be controlled based on the logistics degree of the main 14G and the ff(4), and is separated into the main road. 14〇 and in the embodiment, the bypass tube 141 contains a higher 4 = again: combination than the ethanol mixture stream 143, and the mixture of the product and the ethanol has a total water concentration greater than the centroid ratio, which is greater than 2 wt.% or greater than 5 Μ %. In terms of range, group 5 is from 〇·5 to 15... such as from 2 to (4); Ϊ: 5 to 1 〇wt.% 〇 bypass tube 141 meat staining > In the alternative embodiment, additional water can be added to the second distillation column 1〇9 via line (2). Alternatively, individual columns of the internal stream of water stream 142 may be added, which may be selected from any of the four distillation columns that perform the separation and/or purification steps of the particular 27 201245120. Preferred are individual columns: having (1) 50 trays, for example: from 1 to (10) trays or trays from 30 to 75 trays. The tray may be the remaining tray, the fixed tray' or any of the metering towers known to the art. _ domain na μ, gauge _4^^= can be used. & Private or Herco may be placed in a continuous steaming tower, or a steaming one that may be placed in two or more seats, which allows the second seat to enter the second seat from the second seat. Enter the first seat and so on. For the sake of convenience, the first - column and the _ thing can also be called the second or "first-residue,". Other museums or residues of the steaming tower can also have similar = repair, language (Second 'third, etc.') to distinguish each other, but such revisions should not be interpreted as requiring any particular separation order. The associated condenser and liquid separation tanks for each - steamed tower can be any The traditional setting =, ' is simplified in the drawing. Heat can be supplied to the bottom of each steaming tower or the bottom can be flowed through % by heat exchange H or re-riding. Also depends on other _ (4), such as internal reboil The heat supplied to the reboiler can be derived from the heat generated in any process, and the process can be integrated with the reboiler or dispensed with the surface, such as other chemical processes or steel furnaces that generate heat. A reaction-reaction-flash column, but in some embodiments of the invention, a reaction H, a flash column, a cold wire, a heating element, and other components can be finely added. It is known to those skilled in the art that Various condensers, pumps, compressors, reboilers, and drums for chemical processes , valves, connectors, separation vessels, etc., can also be combined and used in the process of the invention. The temperature and pressure used for the steaming tower may vary. In terms of practical problems, although in some implementations Shooting can be a shame of Weiqin (subatmQspheriepres_s) or super atmospheric pressure, but the pressures generally used in these areas range from 10 kPa to 3000 kPa. The temperature in different areas is generally between the removed distillate composition and Between the boiling points of the residue composition removed. It is known to those skilled in the art that the temperature at a point in the operation of the distillation column is dependent on the composition of the material at that location and the pressure of the column. In addition, depending on the manufacturing process The feed rate may vary depending on the size, and if stated, 28 201245120 may be expressed in a general manner in a feed weight ratio. The ethanol composition produced in the embodiments of the present invention may be suitable for a variety of applications, _, chemical raw materials, pharmaceuticals, detergents, disinfectants, gas delays 费 'fee. In fuel applications, the completed ethanol composition can be mixed with gasoline for maneuvering, carrying tools, such as Automobiles, boats and small piston engine aircraft. In the application of the ingredients, the finished ethanol composition can be used as a solvent, detergent, disinfectant, material, ink, and medicine for cosmetics and beauty preparations. The product can also be used as a process solvent for pharmaceutical production. σ, food preparation, dye, photochemical and latex processing manufacturing process. Any of the ethanol composition can also be used as a chemical raw material to make other chemical materials such as =,乙乙乙, 乙乙,乙乙,乙二乙,乙胺,面,和高醇醇三, especially butanol. In the production of acetic acid ethyl s, the completed ethanol composition can be obtained by acid In another application, the completed ethanol composition can be dehydrated to produce ethylene. Any dehydration touch can be used to dehydrate the ethanol, as described in the Laiwu Patent Publication No. 2010/0030002 and 2010/. 0030001 t, the entire contents of which are hereby incorporated by reference. Buddha stone touch, for example, can be used as a media. Preferably, the zeolite has a pore diameter of at least about 〇6 nm, and preferably the stagnation stone comprises a dehydration catalyst, which is selected from the group consisting of mordenite 'ZSM-5'; X, for example, is described in the patent application No. 2,882,244 and the zeolite γ is described in Leo 3, DO, No. 0, the entire contents of which are incorporated herein by reference. In order to more effectively understand the invention as disclosed herein, the embodiments are provided below. It should be understood that these embodiments are only for the sake of the ship, and in any case, the ship is not limited to invention. [Embodiment] Examples The following examples are a composition of a material and a separation system. ASPENP1US 7" simulation software was prepared to test various advances. 201224120 Example 1 included 56% by weight of ethanol '38% by weight of water, 2% by weight. The reaction product of 2% by weight of acetaldehyde '1% by weight of acetic acid, and 丨% by weight of other organics was fed into a distillation column at 10 lbs per hour. The distillation column operates at atmospheric pressure with a 5 Torr tray. The feed tray is located on the 35th tray from the top. Table 6 compares the difference between two different operations = Cheng. The energy requirement per ton of refined ethanol in operation A is about 5 times greater than that of operation b.
實施例2 步分離來贼乙醇的乙醇混合物。勉_者的水移除以生產可以進- 水分離器 分子篩 表7 膜 乙醇混合物 乙醇 93.2重量％ 水 醋酸乙酯 0.2重量％ 33重量％ 89.9重量％ 3.8重量％Example 2 An ethanol mixture of thief ethanol was separated.勉 _ water removal to produce a feed-water separator molecular sieves Table 7 membrane ethanol mixture ethanol 93.2% by weight water ethyl acetate 0.2% by weight 33% by weight 89.9% by weight 3.8% by weight
S 30 201245120 實施例3 包括56莫耳％( m〇l.%)的乙醇，38 md.%的水，2 m〇1 %醋酸乙 酉旨’ 2 mol·%的乙駿，1 m〇l.%的醋酸’以及1 mol.%其他的有機物之反 應產物饋入一個含有PSA之蒸餾塔來加工餾出物之分流。蒸鶴塔以37 塔盤在大氣壓力下運作且進料塔盤座落於從頂部之第17個塔盤蒸德 塔以135.8 kPa(千巴)以及塔頂為89°C且殘留物為12(TC的溫度^運 作。館出物分流成相等部份(1:1)以及一個部份的館出物係饋入至在 52°C的溫度與34.5迚3的壓力下運作之psA單元。另一部份的餾出 物係與乾乙醇流組合以形成可以於輕餾份蒸餾塔内加工的第二進料。 *如表8所顯示的，蒸餾塔的能量需求隨回流比而變化。能量係以 蒸館塔内百萬英麵量單位每彌製的乙醇為基準。具有最高的回流 比之運作C展現出最高的能量。較低回流比會有更多的水延續至第二 進^牛例如，運作D'E，*F、然而，此蒸娜節’、的能量足以允許 =一步的加工。此外，於輕餾份蒸餾塔内存在的水可能有利於使輕有 =、醋酸乙醋與乙酿和乙醇分離。運作G和H根據由AspEN咖7. i 之模擬展現出低的能量，但是醋酸的量亦大於運作D、E，和F。 31 201245120 表8 :高醋酸轉化率（99%) 運作C 運作D 運作E 運作F 運作G 運作Η 餾出物-重量％ 乙醇 84.9 83.6 80.8 74.3 73.6 73.1 水 7.4 8.9 12.0 19.0 19.8 20.4 醋酸乙酯 3.0 3.0 2.9 2.7 2.6 2.6 乙醛 2.3 2.2 2.2 2.0 2.0 2.0 醋酸 <0.01 <0.01 <0.01 <0.01 0.03 0.06 分流 1:1 1:1 1:1 1:1 1:1 1:1 回流比 5:1 2:1 3:4 1:10 1:20 1:100 能量（百萬英制熱 量單位/每噸乙醇） 9.74 5.06 3.18 2.33 2.26 2.20 乾乙醇流-重量％ 乙醇 91.7 91.7 91.7 91.6 91.5 91.5 水 0.1 0.1 0.1 0.2 0.2 0.3 醋酸乙酯 3.3 3.3 3.3 3.3 3.3 3.3 乙醛 2.5 2.5 2.5 2.5 2.5 2.5 水流-重量％ 水 98.8 99.0 99.3 99.6 99.6 99.6 乙醇 1.1 0.9 0.7 0.4 0.4 0.4 第二進料-重量％ 乙醇 89.7 88.9 87.3 83.4 83.0 82.6 水 3.6 4.4 6.2 10.3 10.8 11.2 醋酸乙酯 3.2 3.1 3.1 2.9 2.9 2.9 乙醛 3.1 3.0 3.0 2.9 2.8 2.8S 30 201245120 Example 3 comprises 56 mol% (m〇l.%) of ethanol, 38 md.% of water, 2 m〇1% of ethyl acetate, '2 mol·% of B, 1 m〇l. The reaction product of % acetic acid' and 1 mol.% of other organics is fed to a distillation column containing PSA to process the diversion of the distillate. The steaming crane tower operates at 37 atmospheres at atmospheric pressure and the feed tray is located at the top of the 17th tray steamed tower at 135.8 kPa (kilobar) and the top of the tower at 89 °C with a residue of 12 (TC temperature ^ operation. The museum output is divided into equal parts (1:1) and a part of the museum output is fed to the psA unit operating at a temperature of 52 ° C and a pressure of 34.5 迚 3 . Another portion of the distillate is combined with the dry ethanol stream to form a second feed that can be processed in the light ends distillation column. * As shown in Table 8, the energy demand of the distillation column varies with the reflux ratio. The energy is based on the amount of ethanol per milligram of the unit in the steaming tower. The operation with the highest reflux ratio shows the highest energy. The lower reflux ratio will have more water to continue into the second. ^ Cattle, for example, operates D'E, *F, however, this steaming section's energy is sufficient to allow = one-step processing. In addition, the water present in the light ends distillation column may be beneficial to make light =, acetic acid Ethyl vinegar is separated from B and Ethanol. Operation G and H show low energy according to the simulation by AspEN Coffee 7. i, but the amount of acetic acid is also large. Operation D, E, and F. 31 201245120 Table 8: High Acetic Acid Conversion (99%) Operation C Operation D Operation E Operation F Operation G Operation 馏 Distillate - Weight % Ethanol 84.9 83.6 80.8 74.3 73.6 73.1 Water 7.4 8.9 12.0 19.0 19.8 20.4 Ethyl acetate 3.0 3.0 2.9 2.7 2.6 2.6 Acetaldehyde 2.3 2.2 2.2 2.0 2.0 2.0 Acetic acid <0.01 <0.01 <0.01 <0.01 0.03 0.06 Split 1:1 1:1 1:1 1:1 1: 1 1:1 reflux ratio 5:1 2:1 3:4 1:10 1:20 1:100 energy (million British thermal units per ton of ethanol) 9.74 5.06 3.18 2.33 2.26 2.20 dry ethanol flow - wt% ethanol 91.7 91.7 91.7 91.6 91.5 91.5 Water 0.1 0.1 0.1 0.2 0.2 0.3 Ethyl acetate 3.3 3.3 3.3 3.3 3.3 3.3 Acetaldehyde 2.5 2.5 2.5 2.5 2.5 2.5 Water flow - wt% Water 98.8 99.0 99.3 99.6 99.6 99.6 Ethanol 1.1 0.9 0.7 0.4 0.4 0.4 Second Material-% by weight Ethanol 89.7 88.9 87.3 83.4 83.0 82.6 Water 3.6 4.4 6.2 10.3 10.8 11.2 Ethyl acetate 3.2 3.1 3.1 2.9 2.9 2.9 Acetaldehyde 3.1 3.0 3.0 2.9 2.8 2.8
32 S 201245120 ，蒸鱗内所需的能量以從顧出物移除水，饋入至第― ϊίϋΓ藉她_PSA^㈣的純綱彳。 ::另:Γ施方式可㈣::二中對 者將能理解。再者，對此領域之熟悉技藝者=明白 刖田％、疋制列說明，不是為了限制本發明保護範圍。 【圖式簡單說明】 種實施方式_細解說結合附圖可更徹底 了解本發明’其中相同之數字係指相同的元件。 第1圖顯示-種按照本發明—實施方式的乙醇生麵統流程圖， 該乙醇生產系統具有供用於由第—館出物移除水之水分離器。 第2圖顯種觀本㈣―實施方式的乙醇生產彳、統流程圖， 該乙醇生產系統具有供用於由第一餾出物移除水之膜。 第3圖顯示-種按照本發明一實施方式的水分離器之旁通管流程 圖’其供用於由第一餾出物移除水。 ；1 【主要元件符號說明】 代號 說明 100 系統 101 反應區 102 分離區 103 反應器 104 管路/氫氣進料 33 201245120 代號 說明 105 管路/醋酸進料 106 分離器 107 蒸餾塔/第一蒸餾塔 108 管路 109 第二蒸餾塔/蒸餾塔 110 蒸發器 111 管路 112 管路 113 蒸氣流 114 液體流/管路 115 管路/蒸餾塔 116 管路 117 管路/冷凝管路/第一餾出物 118 水分離器/蒸餾塔 119 水流 120 乙醇混合物流 121 管路 122 管路 123 管路/第二餾出物 130 壓縮器 131 膜 132 滲透物流 133 管路 134 滯留物流32 S 201245120 The energy required in the steamed scale is to remove the water from the take-up and feed it to the pure 彳 of the _PSA^(4). ::Other: The implementation method can be (4):: The second middle will understand. Furthermore, those skilled in the art will understand that the present invention is not intended to limit the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be more fully understood from the following detailed description. Figure 1 shows a flow chart of an ethanol production system according to the present invention, which has a water separator for removing water from the first library. Fig. 2 is a schematic diagram showing the ethanol production system of the embodiment (4), which has a membrane for removing water from the first distillate. Figure 3 shows a bypass flow diagram of a water separator in accordance with an embodiment of the present invention for use in removing water from a first distillate. ;1 [Main component symbol description] Code description 100 System 101 Reaction zone 102 Separation zone 103 Reactor 104 Pipeline / hydrogen feed 33 201245120 Code description 105 Pipeline / acetic acid feed 106 Separator 107 Distillation column / first distillation column 108 Line 109 Second Distillation Tower / Distillation Column 110 Evaporator 111 Line 112 Line 113 Flow of Steam 114 Liquid Stream / Line 115 Line / Distillation Column 116 Line 117 Line / Condensation Line / First Distillate 118 Water separator/distillation column 119 Water stream 120 Ethanol mixture stream 121 Line 122 Line 123 Line/second distillate 130 Compressor 131 Membrane 132 Permeate stream 133 Line 134 Retentate
34 201245120 代號 說明 140 主管路/物流 141 旁通管/物流 142 水流 143 乙醇混合物流 3534 201245120 Code Description 140 Main Line / Logistics 141 Bypass / Logistics 142 Water Flow 143 Ethanol Mixture Flow 35
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|---|---|---|---|
| US13/094,657US8754268B2 (en) | 2011-04-26 | 2011-04-26 | Process for removing water from alcohol mixtures |
| PCT/US2011/059891WO2012148459A1 (en) | 2011-04-26 | 2011-11-09 | Process for removing water from ethanol mixtures |
| Publication Number | Publication Date |
|---|---|
| TW201245120Atrue TW201245120A (en) | 2012-11-16 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101110996ATW201245120A (en) | 2011-04-26 | 2012-03-29 | Process for removing water from alcohol mixtures |
| Country | Link |
|---|---|
| US (1) | US8754268B2 (en) |
| EP (1) | EP2702019A1 (en) |
| CN (1) | CN103068782B (en) |
| AR (1) | AR086054A1 (en) |
| BR (1) | BR112013027176A2 (en) |
| MX (1) | MX2013012533A (en) |
| TW (1) | TW201245120A (en) |
| WO (1) | WO2012148459A1 (en) |
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